Catalysis and Automotive Pollution Control III (Studies in Surface Science and Catalysis, Volume 96)

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Studies in Surface Science and Catalysis 96 CATALYSIS AND AUTOMOTIVE POLLUTION CONTROL III

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Studies in Surface Science and Catalysis Advisory Editors: B. Delmon and J.T. Yates

Vol. 96

CATALYSIS AND AUTOMOTIVE POLLUTION CONTROL III Proceedings of the Third International S y m p o s i u m (CAPoC 3), Brussels, Belgium, April 20-22,1994 Editors

A. Frennet and J.-M. Bastin

Catalyse H6t6rogene, Universit6 Libre de Bruxelles, Brussels, Belgium

ELSEVIER Amsterdam - L a u s a n n e - New Y o r k - Oxford - Shannon - S i n g a p o r e - T o k y o

ELSEVIER SCIENCE B.V. Sara Burgerhartstraat 25 P.O. Box 211, 1000 AE Amsterdam, The Netherlands

First printing: 1995 Second impression: 1998

ISBN 0-444-82019-1 9

1995, ELSEVIER SCIENCE B.V. All rights reserved.

No part of this publication may be reproduced, stored in a retrieval system or transmitted in any form or by any means, electronic, mechanical, photocopying, recording or otherwise, without the prior written permission of the publisher, Elsevier Science B.V., Copyright & Permissions Department, P.O. Box 521, 1000 AM Amsterdam, The Netherlands. Special regulations for readers in the U.S.A.-This publication has been registered with the Copyright Clearance Center Inc. (CCC), 222 Rosewood Drive Danvers, MA 01923. Information can be obtained from the CCC about conditions under which photocopies of parts of this publication may be made in the U.S.A. All other copyright questions, including photocopying outside of the U.S.A., should be referred to the copyright owner, Elsevier Science B.V., unless otherwise specified. No responsibility is assumed by the publisher for any injury and/or damage to persons or property as a matter of products liability, negligence or otherwise, or from any use or operation of any methods, products, instructions or ideas contained in the material herein. This book is printed on acid-flee paper Printed in The Netherlands

CONTENTS

PRELIMINARIES

Foreword ...................................................................................... Acknowledgments .......................................................................... Financial Support ........................................................................... Committees ................................................................................... GENERAL LECTURES . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

xiii xv xvi xvii 1

Automotive and Environment: Towards a Global Approach. D. Savey .......................................................................................

3

Developments in Gasoline reformulation and The Enhancement o f Refinery MTBE Production K.P. de Jong, W. Bosch and T.D.B. Morgan .....................................

15

Internal Combustion Engines Probable Evolutions and Trends. P. Eyzat ........................................................................................ MODEL REACTIONS & MODEL CATALYSTS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

33 53

Laboratory Data for Three-Way Catalytic Converter Modeling. D. Sehweieh ..................................................................................

55

Reactivity of Steam in Exhaust Gas Catalysis. Part II: Sintering and Regeneration of Rh and PtRh Catalysts in Propane Oxidation. J. Barbier Jr. and D. Duprez ...........................................................

73

An Infrared Study of CO and NO Adsorption on Pt, Rh, Pd 3-Way Catalysts. R.L. Keiski, M. H~irk6nen, A. Lahti, T. Maunula, A. Savim~iki and T. Slotte ......................................................................................

85

Comparative Behaviour of Pd Supported Catalysts for the Reduction of NO by CO in the Presence of Gas Complex Mixture Including 02, C02, H20 and Hydrocarbons. A. Lemaire, J. Massardier, H. Praliaud, G. Mabilon and M. Prigent ... 97

XPS/TPR Study of the reducibili~ of M/Ce02 catalysts (M=Pt, Rh): Does Junction effect theory apply? J.P. Holgado and G. Munuera ..........................................................

109

vi

Enhancement of the Reaction of Nitric Oxide and Carbon Monoxide by Hydrogen and Water over Platinum and Rhodium - Containing Catalysts. R. Dtimpelmann, N.W. Cant and D.L. Trimm .................................. 123

Simultaneous NO x Reduction and Soot Elimination from Diesel Exhaust on Perovskite-Type Oxide Catalysts. V. Duriez, L. Monceaux and P. Courtine ......................................... 137

How a Three-Way Catalyst is Affected under Transient Conditions: A Study of Pt-Rh/Al203 Catalyst. C. Howitt, V. Pitchon, F. Garin and G. Maire ................................... 149

Comparison of Pt/MnOx/Si02 and Pt/CoOx/Si02 Catalysts for the CO Oxidation with 02 and the NO Reduction with CO. Y.J. Mergler, A. van Aalst, J. van Delft and B.E. Nieuwenhuys .......... 163

Reduction Behavior of Rh-Sn/Si02 Bimetallic Catalysts and its CO Oxidation Activity. S. Nishiyama, I. Yamamoto, M. Akemoto, S. Tsuruya and M. Masai... 179

Preparation of Pt-Rh/A1203-CeO 2 Catalysts by Surface Redox Reactions. L. Pirault, D. El Azami El Idrissi, P. Mar6eot, J.M. Dominguez, G. Mabilon, M. Prigent and J. Barbier ............................................. 193

Reactivity of Perovskites as Automotive Converters. L. Simonot, F. Garin and G. Maire .................................................. 203

Effect of the CeO 2 Dispersion on Alumina on its Reactivi~. for CO and NO Conversion. R. Catalufia, A. Arcoya, X.L. Seoane, A. Martinez-Arias, J.M. Coronado, J.C. Conesa, J. Sofia and L.A. Petrov ....................... 215

Mechanism of Chemical Activation of Pt-Rh Alloy and Pt-Rh Bimetallic Single Crystal Surfaces. Hiroyuki Tamura, Akira Sasahara and Ken-iehi Tanaka ..................... 229

Changes in Microstructure and Catalytic Activi~. Effected by Redox Cycling of Rhodium upon CeO 2 and Al203. J. Cunningham, D. Cullinane, F. Farrell, M.A. Morris, A. Datye and D. Lalakkad ............................................................................ 237

oo

Vll

Catalytic Oxidation of Propane over Palladium Supported on Alumina Aerogel. Effects of the Pretreatment on the Activity and Investigation of the State of Palladium by Grazing- Incidence-XRay Diffraction. C. Hoang-Van, R. Harivololona and S. Fayeulle ................................ 249

Characterization of Surface and Bulk Oxygen Species of Three Way Catalysts by 02 TPD and H2 TPR. C. Bouly, K. Chandes, D. Maret and D. B ianchi ................................ 261

The Oxidation of Carbon Monoxide by Oxygen over Polycrystalline Platinum, Palladium and Rhodium from UHV to Normal Pressure. S. Fuchs and T. Hahn ................................................................... 275

Oxidation and Disproportionation of Carbon Monoxide over Pd/ZrO 2 Catalysts Prepared from Glassy Pd-Zr Alloy and by Coprecipitation. S. Gredig, S. Tagliaferri, M. Maciejewski and A. Baiker ................... 285

Combustion of M-Xylene over Amorphous Pd2Ni50Nb48 Alloy.

Pd

Catalysts derived from

L. Bork6, Hua Zhu, Z. Schay, I. Nagy, A. Lovas and L. Guczi .......... 297 SUBSTRATES

~g~

WASHCOAT TECHNOLOGIES . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

305

Design and Performance of a Ceramic Preconverter System. S.T. Gulati, L.S. Socha and P.M. Then ............................................. 307

Improvment of the Thermal Stability of Ceria Support. M. Pijolat, M. Prin, M. Soustelle, O. Touret and P. Nortier ............... 325

Radial Flow Converter: New Developments in High Cell Density Catalysts F. Bonnefoy, F. Petitjean and P. Steenackers .................................... 335

Stabilization of Rhodium~Alumina Catalysts by Silicon Exchange. R.W. MeCabe, R.K. Usmen, G.W. Graham, W.L.H. Watkins and W.G. Rothschild ...................................................................... 347

Structural, Morphological and Surface Chemical Features of A120 3 Catalyst Supports Stabilized with Ce02. C. Morterra, G. Magnacca, V. Bolis, G. Cerrato, M. Bariceo, A. Giachello and M. Fueale ............................................................. 361

viii

Support and NEMCA Induced Promotional Effects on the Activity of Automotive Exhaust Catalysts. I.V. Yentekakis, C.A. Pliangos, V.G. Papadakis, X.E. Verykios and C.G. Vayenas .......................................................................... 375

Synthesis and Study of Honeycomb Monolithic Catalysts f o r Catalytic Combustion. Z.R. Ismagilov, G.V. Chernykh and R.A. Shkrabina ......................... 387

Structure and Catalytic Activity of Mixed Oxides of Perovskite Structure. V. Mathieu-Deremince, J. B. Nagy and J.J. Verbist ........................... 393

Preparation of Alumina Supported Ceria. I: Selective Measurement of the Surface Area of Ceria and Free Alumina. R. Fr6ty, P.J. Levy, V. Perrichon, V. Pitchon, M. Primet, E. Rogemond, N. Essayem, M. Chevrier, C. Gauthier and F. Mathis... 405

Influence of the Nature of the Metal Precursor Salt on the Redox Behaviour of Ceria in Rh/CeO 2 Catalysts. S. Bernal, J.J. Calvino, G.A. Cifredo, J.M.Gatica, J.A. P6rez Omil, A. Laachir and V. Perrichon ........................................................... 419

The Preparation of Thermally Stable Washcoat Aluminas from Low Cost Gibbsite. Yafeng Huang, N.W. Cant, J. Guerbois, D.L. Trimm and A. Walpole .............................................................................. 431 GASOLINE CATALYST TECHNOLOGIES. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

439

Development of Improved Pd-only and Pd/Rh Three-Way Catalysts. B.H. Engler, D. Lindner, E.S. Lox, A. Sch~ifer-Sindlinger and K. Ostgathe ............................................................................. 441

Smart Pd TWC Technology to Meet Stringent Standards. J. Dettling, Z. Hu, Y. K. Lui, R. Smaling, C. Z. Wan and A. Punke .... 461

A Palladium Front Brick Study. D.J. Ball and E. Jacque ................................................................... 473

Non-Noble Metal Environmental Catalysts: Synthesis, Characterization and Catalytic Activity. P.G. Harrison,N.C. Lloyd and Wan Azelee ....................................... 487

ix DIESEL CATALYST TECHNOLOGIES . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

497

Catalytic Oxidation of Diesel Particulates with Base Metal Oxides. K.E. Voss, J.K. Lampert, R.J. Farrauto, G.W. Rice, A. Punke, and R. Krohn ................................................................................ 499

Performance of Oxidation Catalysts for HeavT-Du~. Diesel Engines. H.J. Stein, G. Htithwohl and G. Lepperhoff ...................................... 517

Catalytic Reduction of Nitrogen Oxides in Diesel Exhaust Gas. B.H. Engler, J. Leyrer, E.S. Lox and K. Ostgathe ............................. 529

Catalytic Oxidation of Diesel Soot: Catalyst Development. J.P.A. Neeft, O.P. van Pruissen, M. Makkee and J.A. Moulijn ............ 549

Catalytic Combustion of Diesel Soot on Perovskite Type Oxides. W. S ri Rahayu, L. Moneeaux, B. Taouk and P. Courtine ................... 563 LEAN NOx CATALYST TECHNOLOGIES . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

575

The Mechanism of the Lean NOx Reaction over Pt-based Catalysts. G.P. Ansell, S.E. Golunski, J.W. Hayes, A.P.Walker, R. Bureh and P.J. Millington ......................................................................... 577

Influence of the Copper Dispersion on the Selective Reduction o f Nitric Oxide over Cu/AI203 : Nature of the Active Sites. Z. Chajar, M. Primet, H. Praliaud, M. Chevrier, C. Gauthier and F. Mathis ................................................................................ 591

Lean NOx reduction on Cu-NaY and Cu-HZSM5 Zeolites at the Spark Ignition Engine Exhaust. P. Ciambelli, P. Corbo, M. Gambino, V. Indovina, G. Moretti and M.C. Campa ............................................................................ 605

Oxidation State of Copper During the Reduction of NOx with Propane on H-Cu-ZSM5 in Excess Oxygen. T. Pieplu, F. Poignant, A. Vallet, J. Saussey, J.C. Lavalley and G. Mabilon .............................................................................. 619

NO Decomposition over Containing Catalysts.

Partially Reduced Metallized CeO 2

Gangavarapu Ranga Rao, P. Fornasiero, J. Kaspar, S. Meriani, R. di Monte and M. Graziani ........................................................... 631

Selective Catalytic Reduction of NOx in Diesel Exhaust Gases with Ntt 3 over Ce & Cu Mordenite and V205/TiO2/W03 Type Catalysts: can Ce solve the NH3 slip problem? R.J. Hultermans, E. Ito, A. Jozsef, P.M. Lugt and C.M. van den Bleek ................................................................. 645

Reaction Study of Diesel Exhaust Gases over Copper Oxide Based Model Catalysts. C-M. Pradier, H. Vikstrtim and J.Paul ............................................. 655

Selective Reduction of NOx with Ammonia over Cerium Exchanged Zeolite Catalysts: Towards a Solution for an Ammonia Slip Problem. E. Ito, R.J. Hultermans, P.M Lugt, M.H.W. Burgers, H. van Bekkum and C.M. van den Bleek ........................................... 661

Selective Reduction of NO over Copper Containing Modified Zeolites. J. Halfisz, J. Varga, G. Schtibel, I. Kiricsi, K. Hernfidi, I. Hannus, K. V arga and P. Fejes ......................................................................... 675

Zeolite Catalyst for the Purification of Automotive Exhaust Gases. D. Florea, L. Georgescu, F. Constantinescu, D. M~noiu, D. Gaber and M. Com~nescu ......................................................................... 687

Studies of Selective NO Reduction by CH4 and CH30H over Co and Cu Exchanged Mordenite. J. Vassallo, M. Lezcano, E. Mir6 and J. Petunchi .............................. 697

Sepiolite Based Monolithic Catalysts for the Reduction of Nitric Oxide with Propylene in Oxidising atmosphere. P. Avila, J. Blanco, J.M.R. Bias, O. Ruiz de los Patios and M. Yates ... 707 CATALYST AGING

&POISONING

.............................................

719

Impact of Sulfur on Three- Way Catalysts: Comparison of Commercially Produced Pd and Pt-Rh Monoliths. D.D. Beck and John W. Sommers .................................................... 721

An X-Ray Absorption Spectroscopic Investigation of Aged Automotive Catalysts. F. Maire, M. Capelle, G. Meunier, J.F. Beziau, D. Bazin, H. Dexpert, F. Garin, J.L. Schmitt and G. Maire ............................... 749

xi

Sulfur Adsorption and Desorption on Fresh and Aged Ce-Containing Catalysts. S. Lundgren, G. Spiess, O. Hjortsberg, E. Jobson, I. Gottberg and G. Smedler .............................................................................. 763

Inhibition of Post-Combustion Catalysts by Alkynes: A Clue for Understanding their Behaviour under Real Exhaust Conditions. G. Mabilon, D. Durand and Ph. Courty ............................................ 775

Metal Surface Area Measurement of Fresh and Aged Automotive Catalysts by CO Methanation. R.K. Usmen, R.W. McCabe and M. Shelef. ....................................... 789

Effects of Sintering and of Additives on the Oxygen Storage Capacity of PtRh Catalysts. D. Martin,

R. Taha and D. Duprez ................................................. 801

Study of Hydrocarbons Removal with a Three-Way Automotive Catalyst after Severe Thermal Aging. J.M. Bart, M. Prigent and A. Pentenero ........................................... 813

Simultaneous Atmosphere and Temperature Cycling of Three-Way Automotive Exhaust Catalysts. S. Humbert, A. Colin, L. Monceaux, F. Oudet and P. Courtine ........... 829

The Effect of "Spark Retard" as a Method of Raising Exhaust Gas Temperature for Automotive Catalyst Dyno Ageing. J. Kisenyi, N. Pallin, C. Tooby, R.G. Hurley, P. Atherton and D. W e b b ................................................................................. ALTERNATIVE FUELS &APPROPRIATE CATALYSTS . . . . . . . . . . . . . . . . . . . . . . . . . .

841 853

Control of Unregulated Emissions from Ethanol-fuelled Diesel Engines. A Study of the Effect of Catalyst Support on the Low Temperature Oxidation of Ethanol and Acetaldehyde using Precious Metals. L.J. Pettersson, S.G. J~ir~s, S. Andersson and P. Marsh ...................... 855

Catalysts for Natural Gas Emission Control Applications. R.G. Silver and J.C. Summers ........................................................ 871

.~

Xll

MISCELLANEOUS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

885

Modelling Three-Way Monolithic Catalytic Converter: Comparison between Simulation and Experimental Data. S. Siemund, D. Schweich, J.P. Leclerc and J. Villermaux ................... 887

Behaviour of Three-Way Catalysts in a Hybrid Drive System'. Dynamic Measurements and Kinetic Modelling. S. Tagliaferri, L. Padeste and A. Baiker ........................................... 897

The Performance of a Monolithic Catalytic Converter o f Automobile Exhaust Gas with Oscillatory Feeding of CO, NO and 02: a modelling study. A.J.L. Nievergeld, J.H.B.J. Hoebink, G.B. Marin .............................. 909

Cold Start Hydrocarbon Emissions Control via Admixing Three Way Conversion Catalysts with Heat Exchange and Hydrocarbon Adsorption Phenomena. P.L. Burk, J.K. Hochmuth, D.R. Anderson, S. Sung, A. Punke, U. Dahle , S.J. Tauster, C.O. Tolentino, J. Rogalo, G. Miles, M. Mignano and M. Niejako ........................................................... 919

AUTHOR INDEX . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

931

xiii

FOREWORD This Congress is the third edition of a series of Symposia devoted to the use of catalysis for the depollution of the exhaust gases of motor vehicles. As the first two of these meetings, it took place at the ~ Universit6 Libre de Bruxelles )), April 20-22, 1994. In spite of the number of years that catalysts started to be developped for this purpose (from the early seventies) the important economical impact of the problem makes it still a topic of the day. This is namely revealed by the increasing number of submitted, accepted and published papers, as it appears in the following table: Papers

Submitted

Accepted

CAPoC 1 CAPoC 2 CAPoC 3

38 66 131

42 79

Presented and published 28 34 67

General Lectures. 9 4 4

It has been a hard task for the paper selection committee to select the proposed presentations. The high quality of the submitted extended abstracts lead this committee to accept for presentation 79 papers from the 131 ones submitted. In practice, from the accepted papers, 12 were not delivered. This was due to the impossibility of some authors to attend the meeting. These papers are not published in the proceedings. The very large number of accepted communications resulted in the organization of a poster session. Anyway, as announced in the circulars, no discrimination is made in these proceedings between the colmnunications presented orally or as a poster. In these proceedings, the papers are grouped into the following headings: 1.Model reactions and model catalysts. 2.Substrates and washcoat technologies 3.Gasoline catalysts technologies 4.Diesel catalyst teclmologies 5.Lean NOx catalyst technologies 6.Catalyst ageing and poisonning 7.Alternative fuels and appropriate catalysts 8.Miscellaneous

xiv It is interesting to notice that 25 presented and published papers are coming from industries, and 42 from Universities and Research Institutes. On the other hand the number of registered and invited participants was of 279, within which the number of academic people (79 from Universities + 40 from Research Institutes) and industrial representatives (133) was about equivalent. Most of these participants came from western Europe: France (71), Belgium (51), Germany (33), Great Britain (27), The Netherlands (17), Sweden (14), Italy (10), Spain (4), Finland (4), Luxembourg (3), Denmark(1 ), Greece ( 1), Ireland (1). Only 8 participants were from the former east block: Hungary (6), Russia(I), Roumania (1). Eighteen participants came from the U.S.A. and finally let us mention 4 attendants from Australia, 2 from Japan and one from South Africa and from Argentina. The large number of answers to the questionnaire distributed to the participants at the end of the Congress contained strong encouragement to continue the series of these ~ CAPoC ~ meetings. The organizers. J.-M. BASTIN Secretary of the Organizing Committee

A. FRENNET Chairman of the Organizing Committee

XV

ACKNOWLEDGMENTS The organizers are indebted to the authorities of the for their hospitality and for the welcome address made by the reprensentative of the Rector of the University. They also greatly appreciate the cooperation of the members of the organizing committee and the paper selection committee, namely for their important contribution in selecting the proposed papers. Special thanks are due to all lecturers of the introductory session: K.C.Taylor, K.P. de Jong, P. Z. Eyzat and D. Savey for the high quality of their contribution. It is also a pleasant duty to thank all the members of the ~~of the Universit~ Libre de Bruxelles for their help in organizing this congress. We are in particular very much indebted to BOatrice Depuydt-Parmentier and Axel L6fberg for their continuous active involvement in solving various material problems. The organizers want to recognize the important, but sometimes hidden, contribution of Mrs.Frennet to the succes of the symposium. The scientific quality of the Congress is certainly for an important part due to the quality of the contributions of both the authors and the participants in the discussions. They all contributed to the success of the Congress. Thanks to all of them. J.-M. BASTIN Secretary of the Organizing Committee

The organizers. A. FRENNET Chairman of the Organizing Committee

xvi

FINANCIAL SUPPORT

The following companies have accepted to provide financial support to this Congress. The Organizers express their gratitude to these companies for their generosity. AlliedSignal Inc. Degussa AG Ford Motor Co General Motors Luxembourg Johnson Matthey Ltd

xvii

ORGANIZING COMMITTEE Chairman :

FRENNET A. Universit6 Libre de Bruxelles Secretat T :

BASTIN J-M. Universit6 Libre de Bruxelles Members :

CAMP~ M. Ecole Royale Militaire CUCCHI C. ACEA DEROUANE E. Facult6s Universitaires Notre Dame de la Paix ENGLER B. Degussa AG ESPRIT M. Union Mini6re GAGNERET P. Allied Sigaml Enviromnetal Catalysts GERMAIN A. Universit6 de Li6ge GERRYN C. HECQ W. Universit6 Libre de Bruxelles JANNES G. C.E.R.I.A. - Institut Meurice KONIG A. Volkswagen AG KUPE J. General Motors Luxemburg LEDUC B. Universit6 Libre de Bruxelles NIEUWENHUYS B. Rijksuniversiteit Leiden PENTENERO A. Universit6 de Nancy PONCELET G. Universit6 Catholique de Louvain PRIGENT M. Institut Frangais du P6trole SCHWEICH D. LSGC-ENSIC WEBSTER D. Jolmson Matthey LTD

PAPER SELECTION COMMITTEE All members o f the organizing committee, and

BELOT G. Peugeot S.A. BRUNELLE J.P. Rhone Poulenc GARIN F. Universit6 de Strasbourg LECLERCQ L. Universit6 de Lille PONEC V. Rijksuniversiteit Leiden


General Lectures


A. Frennet and J.-M. Bastin (Eds.) Catalysis and Automotive Pollution Control III Studies in Surface Science and Catalysis, Vol. 96 1995 Elsevier Science B.V.

Automotive and Environment: Towards a global approach Dominique Savey Deputy Managing Director Automotive Division PSA PEUGEOT CITROI~N 75 avenue de la Grande Arm6e 75116 Paris

Thank you for inviting me to join you here at the third international congress on catalysis and automotive pollution control. CATALYSEUR, KATALYSATOR, CATALYST, in the past few years, this equipment has reached a level of public awareness, exceptional for a purely technical device. The catalytic converter gained almost mythical status for a period. People in charge of marketing, people in charge of advertising and politicians seized on the concept to the point where cars were no longer judged on their real pollution emissions but on the one criterium of being fitted or not with a catalytic converter. And in some cases, vehicles bans have been implemented according to this criterium. Rarely has a technical problem of such major economic significance been handled so irrationally. Today, passions have cooled and catalytic converters are no longer a controversial issue. So it is time to take a calm and collected look at environmental problems. So I am pleased that you gave me the opportunity first of all to expose to you the studies that PSA PEUGEOT CITROEN is conducting in this area, secondly to present to you the global approach which we feel is necessary in order to integrate properly the passenger cars in the environment, and finally to tell you about the advances that we, carmarkers, are expecting from the catalyst experts that you are. Since World War II, the usage of motor car has grown tremendously in democratic countries. However, that development raises concerns for the environment because of the nuisance caused by cars. Today, most of those nuisances from cars are on the decrease and this improvement should become more widespread in coming years. I would like to speak of two major types of problems relating to the environment: firstly, air pollution and secondly the consequences on the climate and our natural resources, of the car fuel consumption.

I- On the first point, air pollution, major efforts have been made in the past 20 years to reduce exhaust emissions of new cars, and you have contributed much to this effort. Between 1970 and 1993, the level of legal emission standards in Europe has been devided by between 10 and 20, depending on the pollutant (Figure 1).

Capacity 1,500 cm 3 Inertia 1,130 kg Rase 100 in 1971

Cycle

ECE

' ( cycle

I?CE + EUDC

The emissions of CO and of HC + NOx have diminished since 1970 by more than 90%,

cycle ECE

4

cycle

ECE + EUDC

Figure 1

However, to date, such efforts have only involved new vehicles, and it will take time before the full effects are felt. Since a car's average life is approximately 10 years, and given the time needed for a full-scale replacement of the in-use vehicles, the complete results of new measures are apparent only after about fifteen years, once the majority of old cars have been replaced. Thus, the catalytic converter, which became mandatory in 1993, will make its mark only gradually and will not be fully effective until year 2008 or 2010. Several studies conducted by INRETS (1) for France, the European Union for the 12 European countries, and QUARG (2) for the United Kingdom have analysed this problem and have estimated the evolution of air pollution caused by cars in the coming years. All of them have reached similar conclusions but I will quote the INRETS Study for France, it says that for most pollutants, the global volume of emissions of passenger vehicles on the roads increased regularly, before peaking a few years ago ; now it is declining and should fall even more quickly in the future as old cars will be replaced by new ones. For carbon monoxides (CO), hydrocarbons (HC), volatile organic compounds (VOC), oxides of nitrogen (NOx), lead, sulphur dioxides (SO 2) and aromatic hydrocarbons (HAP) the volume of car exhaust emissions will be cut by at least two thirds by the year 2010 (and some of them will be completely eliminated), despite the fact that road traffic will increase by an estimated 2% per year (see figures 2 and 2a), and without taking in account any further tightening of the European regulation. As a result, the quality of the air in almost all our cities is already improving, due among other things, to the reduction in car exhaust emissions. The improvement is bound to become more widespread in the next 15 years. So today, there is no point imposing ever-stricter standards on new cars which already have extremely low emissions values, and any new measures would be counterproductive in terms of cost-effectiveness because of the almost imperceptible gain in environment that would be achieved. On the contrary, it may be desirable to speed up the pollution reduction process by working on existing cars and to solve any remaining, localised problems by means of better focused measures. I'd like to comment on four types of measures: incentives to speed up the rate of renewal of the existing vehicle fleet, better control of emissions of cars currently on the road, - improve fuel quality, - treatment of urban pollution on a local level, for example through the development of electric and natural gas-powered vehicles for city use or through improved traf~c flow management.

-

-

l

Institut National de Recherches sur le Transport et la S~curit~ Routi~re

2

Safety Research Institute) Quality of Urban Air Review Group

(National Transport and Road

I NOx ( k t ~ 0 12 )

Reneval of the pare by low -emitting vehicles will bring a rapid drop in all pollutants, with an eventual stabilisation at very low levels. Source :LNRETS report 143 (July l991)

Figure 2

40

I

213 '

I

0 1QC+,

LEAD (OC 1985)

lzo

r

11 I

n~

I

on

~ s nI l t ll*sl ~ ~1L"G

wal~ (4s 1gu5I

1

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The emissions of C02 will stabilise and the improvement in fuel qualities will lead to a strong reduction of S02, lead and smoke emissions. Figure 2bis

4

To speed up the renewal of existing cars would be highly desirable because it will have a positive impact on the environment in terms of pollution, noise and fuel consumption. It would also have a positive effect on road safety since new cars are considerably safer than older models. To illustrate the effects of this course of action, a study by Arco showed that by the year 2000, 30% of cars in Europe will not yet be equipped with a catalytic converter and thoses cars would be responsible for more than two-thirds of global automotive pollution (Figure 3). The French government recently announced a programme whereby consumers would be granted a FFr 5,000 subsidy if they trade cars over ten years old for new models. This type of measure ought to be adopted by other European countries.

Stricter periodic technical inspection, especially of emission levels, with the obligation for car owners to rectify any anomalies. This would ensure that existing cars are properly maintained and would make it possible to identify the worst polluters. Studies on vehicles in-use equipped with catalytic converters show that the converters remain effective and reliable as long as they are used and maintained properly. Stricter technical inspection would mean that the On-Board Diagnostic (OBD) system would not be needed to check the functioning of the catalytic converter, the t probe, ignition or canister. In addition to the fact that OBD is not 100% reliable, it is also too expensive for what it is supposed to do given the reliability of today's pollution reduction systems. This has been proven by a number of studies, including one carried out in Switzerland between 1988 and 1990 which examined emissions of 13,000 vehicles equipped with controlled catalytic converters. The study showed that less than one percent of the vehicles monitored exceeded legal limits. Another measure that involves existing vehicles is the improvement of fuel quality. This would immediately and drastically reduce emissions since all vehicles on the road would be affected. European carmakers and oil companies are working together in a European research programme called the European Programme on Emissions Fuels and Engine Technologies (EPEFE). Unfortunately, the programme does not provide for trials on vehicles that do not meet current standards, since this is where the greatest gains could be made. The fourth line of action would be to handle urban pollution problems at the local level and to tailor solutions to the individual problems of each city. This would require analysing and dealing with pollution problems on a needs-specific basis in order to achieve better results. Several solutions will have to co-exist in order to attain maximum efficiency. I shall discuss three of them:

Emissions ( volume )

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By the year 2000, the non catalyst cars will emit 70% of the total emissions while they will constitute only 30% of the parc. Source ARC0 Figure 3

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10 1) In cities and towns, the electric vehicle reduces both pollution and noise while still giving the urban dweller mobility. In addition to being quiet and clean, electric vehicles rely on available energy since batteries would generally be recharged at night, when there is low demand for electricity. Naturally, the vehicles' effect on the environment depends on the type of powerplant that generates the electricity: hydro-electric and nuclear plants cause no pollution, emit no greenhouse gases and protect our natural resources. This is not the case with fuel oil or coal-fired plants. If one million electric vehicles were to be used in Europe, the demand for electricity would equal the production of just one-half of a 900 MW nuclear unit. Therefore, current capacities in off-peak periods would be more than sufficient. Even if, on a European scale, the electricity used by these vehicles were generated by different types of powerplants according the current production parttern, overall carbon dioxide (CO2) emissions would be reduced by 20% compared to gasoline vehicles. PSA Peugeot Citroen was the first among the major car manufacturers to study and develop this type of vehicles in cooperation with component suppliers. Already in 1989, we began selling electric commercial vehicles to city councils and fleet owners in France ; beginning early next year, we will bring electric versions of the Peugeot 106 and the Cito~n AX to market for thoses clients and the private customers. And we plan to launch an entirely new, specifically designed, electric model before the end of the century. Moreover, in the city of La Rochelle, we have been working since last year with the city council and France's electricity utility EDF to test fifty 106s and AXs, which are actually driven by everyday users. 2) In urban areas, vehicles powered by compressed natural gas can also make an important contribution since they cause less pollution than gasoline cars ; because of their greater range, they are more flexible than electric vehicles, but they are not as clean or as quiet. Although the gas solution is less innovative - thousands of natural gas powered vehicles are already on the roads - it is useful in reducing local emissions and diversifying sources of energy. 3) The third solution is to improve traffic flow. Traffic jams cause pollution, increase fuel consumption and waste time. This problem could be improved in two ways: 9 The launch of new road infrastructure programmes: this includes building new motor ways, city bypasses and car parks since insufficient parking space causes additional traffic as drivers are searching for a place to park. 9 The development of traffic management: new technologies offer promising prospects which would optimise the use of road infrastructures by managing traffic flows. This field is extremely vast. It includes : automatic tolls that vary according to day and the time, ~, real-time information on traffic conditions for drivers, information on available parking with remote reservation capability, interactive traffic management to suggest optimised routes based on prevailing traffic conditions. PSA Peugeot Citroen has studied a traffic management system called Isis and is ready to set up pilot operations for validation.

11 I I - T h e second major problem related to environment and caused by passenger cars is the emission of carbon dioxide (C09 and the usage o f non-renewable energy. In fact in Europe cars represent only about 12 % of the emissions of carbon dioxide, but it is essential that everyone make his best effort to reduce these emissions. Car manufacturers have been working for over 15 years to decrease fuel consumption in order to reduce CO 2 emissions and to preserve nonrenewable resources. Efforts have produced significant results since, at PSA Peugeot Citroen for example, average fuel consumption for cars sold in Europe fell by 17% between 1980 and 1990. However, in recent years, anti pollution legislation has opposed our efforts by making mandatory the use of controlled catalytic converters, which increase fuel consumption in gasoline cars. In future, providing that no new legislation gets in our way, further and substantial progress should be possible by expanding the use of diesel in passenger cars, (this is the most effective method of reducing fuel consumption and CO 2 emissions in the short term), by making cars lighter, improving the efficiency of both gasoline and diesel engines and redesigning tyres. PSA Peugeot Citroen has set itself a goal for the year 2000 : average fuel consumption for its cars sold in Europe must be lowered to 6 litres/100 km (47 mpg), i.e. a 15% gain over 1993. In the longer term, we should be able to make even greater progress, and possibly within the next ten years cars consuming less than 3 litres per 100 km (94.2 mpg) will come on the market. Finally, given the expected increase in road traffic, we estimate that fuel consumption for passenger cars will remain globally stable or will decrease over the next ill'teen years. Naturally, most of the measures I have presented to speed up the improvement of air quality would also have positive effects on reductions in fuel consumption and CO 2 emissions.

I'd like now to come back to catalytic converters and present the advances that car manufacturers and customers are expecting from you ; I can see four: 9 9 * 9

substantial cost reduction development of the Denox catalytic converter better light-off from a cold start elimination of hydrogen sulfide (H2S) release

In terms of cost reduction: you know that the use of three-way controlled catalytic converters caused a substantial increase in the price of gasoline cars. In a country such as France, where 80% of new gasoline cars were equipped with a carburettor, the average price increase was 7%. Even though car manufacturers did not pass on the entire cost through to the customer, these higher prices certainly contributed to the current crisis in

12 the car market in Europe. Car is a mass consumer product and it must be affordable to as many consumers as possible. As the passenger car market has developed, so value for money has continuously improved. The catalytic converter costs ten times more per kilogram than the average car on a cost for weight basis. Therefore, it can hardly be considered as an item of equipment for passenger cars since its value for money is far too poor for the customer. It is also fair to question its current environmental costeffectiveness: between the purchase price and the additional fuel consumption, the global annual cost of the catalytic converter and its associated equipments is around 7bn Ecu for carbuyers in the European Union. Therefore, the cost of the three-way catalytic converter must be reduced drastically through technical improvements, and eventually by replacing precious metals with less costly materials. The second area where improvement must be made is in the use of the Denox catalytic converter. You know that one of the drawbacks in the use of a catalytic converter is an increase in fuel consumption. You also know that reducing fuel consumption is one of the primary objectives of European car manufacturers both for environmental reasons and because of customer demand. This can be achieved at the engine level by using diesel technology (indirect injection and more probably direct injection) and by improving combustion in gasoline engines, notably by leaning the fuel/air mixture. In both cases, exhaust levels of oxides of nitrogen (NOx) are increased. The Denox catalytic converter is therefore a key to reducing fuel consumption. Europe must not fall behind in this area given the importance of the diesel engine in our countries. It is unfortunate that there is not a stronger movement on the European level to increase research in this area, as is now the case in Japan. Finally, I would like to mention two problems of a more technical nature: light-off and smells. Under certain conditions, the catalytic converter does not begin operation early enough. This is particularly true in short trips around town, when the engine is cold. Thus, the catalytic converter's effectiveness from a cold start must be improved by speeding-up the light-off process. We must do this without affecting its durability and avoiding solutions which are too complex or costly such as heating the catalytic converter. Since we began equipping our cars with catalytic converters, our customers complain of unpleasant smells primarily during short trips when the car is new. We know that this is caused by hydrogen sulphide (H2S) emissions when the sulphur that accumulates in the catalytic converter is released, and an appropriate solution must be found.

13 To conclude this brief overview, I would like to make two comments: 9 Changes over the past ten years and, even more so, prospects for the future show that the motor car can adapt to environmental requirements. However, it is now time that we tackle problems less emotionally and develop a more rigorous approach: =~ a global approach where governments stop imposing legislation in one area without considering its impact in others, =~ an approach based on cost-effectiveness aimed at organising priorities and selecting appropriate measures, =~ a forward-looking approach so as not to exclude promising technical developments. 9 As far as the catalytic converter is concerned, much progress can still be made and new avenues be explored. Specialists in catalytic converters must be committed to offering significant results as quickly as possible. If we combine these efforts with a global approach, we will produce positive results both for our customers and for the environment.


A. Frennet and J.-M. Bastin (Eds.) Catalysis and Automotive Pollution Control 111 Studies in Surface Science and Catalysis, Vol. 96 1995 Elsevier Science B.V.

15

D E V E L O P M E N T S IN GASOLINE R E F O R M U L A T I O N AND THE E N H A N C E M E N T OF REFINERY MTBE P R O D U C T I O N K.P. de Jong ", W. B o s c h b and T.D.B. M o r g a n r

aKoninklijke/Shell Laboratorium, Amsterdam (Shell Research B. V.), Postbus 38000, 1030 BN Amsterdam, The Netherlands. bShell Internationale Petroleum Maatschappij (B. V.), Postbus 162, 2501 AN The Hague, The Netherlands. CShell Research Ltd, Thornton Research Centre, P.O.Box 1, Chester, Cheshire CH1 3SH, UK ABSTRACT Automotive pollution control calls for joint attention to the three main aspects involved, i.e the fuel, the engine and the exhaust catalyst. In order to establish the potential contribution that gasoline composition can make to reduced emissions in Europe, we present recent data on the relationship between gasoline composition (MTBE, aromatics, olefins) and bulk emissions (HC, CO, NOx). More work is needed to differentiate between the composition and physical properties of the gasoline in these intricate relationships. The relationship between the hydrocarbon emissions ant the gasoline composition, however, is straightforward: for Cs+ species the molecular composition (fingerprint) of the exhaust gas resembles that of the fuel, whereas lighter hydrocarbons in the exhaust gas are combustion products. This conclusion migth be important for further development of exhaust catalysts to cope with the compounds most difficult to convert. The manufacture of MTBE,; one component of US reformulated gasoline is addressed. It is argued that the skeletal isomerisation of n-butenes to isobutene is an attractive route to produce enhanced amounts of MTBE in the oil refinery or chemical complex. Although the rate of MTBE production worldwide has grown rapidly (to 20 Mt/a in 1993) it is still modest in relation to the world demand for gasiline (800 Mt/a). This and the high energy intensity of producing > gasoline components such as MTBE make a ) approach mandatory in optimizing environmental and economic factors. 1.1NTRODUCTION The growing concern about the environment has led to a drastic reduction of emissions from the transport sector. Taking 1968 as a base level for gasoline-fuelled cars, the European commission standards for nitrogen oxides (NOx) and h y d r o c a r b o n s (HC) have

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Figure 1. (a) NOx and (b) hydrocarbons emission standards for cars.

both decreased by 90% (Fig. 1). In the USA, and particularly in California, even more severe standards are being introduced. Between 1970 and 1990 emissions were reduced by the introduction of exhaust catalysts which required unleaded gasoline. However, air quality is still not acceptable in many cities so further measures are needed. The new "Clean Air Act Amendments" of 1990 require both lower vehicle emission limits and the introduction of so-called "reformulated gasoline" in major cities. In Europe there is an ongoing "Tripartite" debate under the leadership of the European Commission and

17 involving the Oil and Motor industries. Its intention is to establish new optimised vehicle emission limits and fuel specifications for the year 2000 in order to improve air quality. In this paper we describe some recent work done by Shell Research (which is submitted to the Tripartite Group) on the effects of gasoline composition and properties on vehicle emissions. In addition the manufacture of MTBE, a relatively new gasoline component and a major feature of US reformulated gasoline is reviewed. Catalysts appear to play an important role in both gasoline manufacture (illustrated for MTBE production) and gasoline end use (exhaust catalysis).

2. DEVELOPMENTS IN GASOLINE REFORMULATION - - USA AND EUROPE In recent years the continuing refinement of engine management and emission control systems has made a significant contribution to lowering tail pipe emissions from gasoline fuelled cars. In the USA, the penetration of cars with catalyst converters is effectively complete. In Europe penetration is around 20% as only recently there has been a requirement for all new cars to be equipped with an exhaust gas catalyst system. Despite these improvements, there is still pressure for further reductions in exhaust emissions. This will require further improvements to vehicles and emission control systems, but attention is also being focused on how changes in the composition and properties of fuels can contribute. In the USA the new 1990 Clean Air Act Amendments require both reduced vehicle emission limits and the introduction of so-called "reformulated gasoline" in cities which do not meet atmospheric ozone targets. Following this legislation, a joint Auto/Oil industry test programme, the Air Quality Improvement Research Programme (AQIRP), has examined the effects of changes in key gasoline properties on emissions from both older and current US vehicles (all catalyst equipped). Using information from this and other programmes, the US Environmental Protection Agency has now published further legislation defining the requirements for reformulated gasoline. This is very complex (some 3000 pages!) but is essentially as follows. Reformulated gasoline must contain a minimum of 2% oxygen, a maximum of 1.0% benzene and no heavy metals but must have detergent additives, while levels of T90, olefins and sulfur must not be higher than each refiners' 1990 average figure (see Table I). In addition, it must meet specified emission targets for VOCs, Table I Reformulated gasoline exemplified m USA: simple model 1995-1997; annual averages (region south) Parameter

Value

Benzene, %vol RVP, psi Oxygen, %w Sulfur, ppmw T90, vol% evaporated Olefins, %vol

< 0.95 < 7.1 > 2.1 * < 100 ** < 100 ** < 100 **

* 2.7 %wt maximum. ** Reference 1990 level (%).

18 air toxics (benzene, 1,3-butadiene, formaldehyde and acetaldehyde) and NOx emissions. These targets are in the form of specified percentage reductions in emissions as compared to the 1990 baseline. The emissions performance of gasolines are calculated on the basis of mathematical models developed using data from the AQIRP and other programmes. The "Simple model", which must be used from 1995-97, specifies fixed RVP limits (assumed to give a 15% reduction in evaporative VOC emissions) and comprises relatively simple equations to calculate air toxic levels. The "Complex model", which must be used from 1998, is a complex set of equations including terms for all major fuel properties, and in many cases second-order terms as well. For further details we refer to [1]. In Europe there is also concern to improve air quality, both local as in the USA and global, i.e. reduced CO2 emission. One sub-group of the Tripartite Group has reviewed the available information (including AQIRP) on the effects of fuel properties, both gasoline and diesel, on vehicle emissions. This has led to the development of a European test programme (EPEFE, the European Programme on Emissions, Fuels and Engine technology), which will cover both gasoline and diesel vehicles and look at effects of specific fuel properties on emissions from advanced technology vehicles. The results from the E P E F E programme are intended to provide a valuable technical input to the European legislative process, which will develop new standards for the year 2000. Shell Research has carried out a major test programme to investigate fuel effects on non-US vehicles. The results from this work have been used as input to the Tripartite investigation and are summarised, together with the results from some other programmes, in the next section.

3. GASOLINE COMPOSITION --- EMISSIONS The work carried out has included two Shell studies. The first was a preliminary study [2] in which 4 cars (1 with a catalyst) were tested over the FTP-75 cycle for regulated and speciated HC emissions on 4 fuels ranging from a conventional to a severely reformulated (research) gasoline. Subsequently, a multi-laboratory study was carried out within the Shell Group to investigate the effect of better controlled step wise changes in gasoline on regulated and speciated HC emissions behaviour, for 24 cars of different engine/catalyst sophistication (and including noncatalyst-equipped cars). The main driving cycle used was the extended European cycle. The work on the regulated emissions has been reported in detail [3]. Figures 2 and 3 summarise the main effects on regulated emissions of varying the key compositional variables, MTBE, aromatics and olefins using paraffins to balance. The designed variations in fuel composition (Table II) inevitably led to changes in other fuel properties especially distillation and stoichiometric air/fuel ratio. The results are given in fleet-averaged form for subsets of noncatalyst- (Fig. 2) and catalyst-equipped cars (Fig. 3). The overall findings show that: (i) Inclusion of MTBE (and removal of paraffins) yields HC and CO reduction benefits in both noncatalyst- and catalyst-equipped cars. (ii) MTBE effects on NOx are small and no clear trend is apparent. (iii) The apparent effect of reducing the aromatics content is to reduce tail pipe HC and CO emissions further, but the accompanying volatility changes in the fuels make the

19

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20

Significant difference from C1 at 95% confidence No significant difference from C 1 at 95% confidence

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21 Table II Composition and properties of test fuels Fuel No. Aromatics, % mass MTBE Olefins T90, ~ E70, %vol

1

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45 15 15 151 30

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reasons for this effect uncertain. It should be noted also that separation of aromatics/ mid-range volatility effects is an objective in the E P E F E gasoline study. (iv) Reducing aromatics content reduces NOx emissions from the noncatalyst-equipped cars, most probably due to an effect on peak combustion temperature, but increases NOx emissions from catalyst-equipped cars, due to reduced catalyst efficiency. Figures 2 and 3 show the car-to-car variability of tail pipe regulated emissions performance, a feature masked by fleet averaging. Variability arises not only in the absolute values of emission levels but also in the response to fuel property changes. The effects of gasoline sulfur on the capacity of the three-way catalyst to control regulated emissions was one of the issues highlighted by the AQIRP programme in which fleet-averaged effects of fuel sulfur were found to be detrimental to the catalytic removal of all three pollutants (VOC, NOx and air toxics). In Fig. 4 we have reproduced data from a recent European study [4] which shows that, as fuel sulfur is increased, HC emissions become higher, CO emissions remain virtually unchanged while NOx emissions are reduced. It is also important to recognise that, even at the 90% confidence interval, statistically significant emission changes are rarely evident. Furthermore, the catalyst composition (its nature and probably also loading of the metals) has a considerable impact. From the foregoing it is clear that the question of sulfur sensitivity requires further clarification, particularly under European conditions, and this is a key technical objective of the EPEFE. From [2] we present further information on the nature (so-called speciation) of the hydrocarbons emissions in the form of the relationship between fuel and exhaust (engineout) composition (Fig. 5). It is evident that the fingerprints for compounds of C5 and higher (C5+) are comparable on a fuel-to-exhaust basis. Thus unburned fuel is a major contributor to the C5+ engine-out profile. Lighter hydrocarbons (C4-) are produced by the breakdown of larger molecules and other partial oxidation products will also form (e.g. aldehydes and ketones, which are not considered here). Figure 6 provides a more quantitative example of exhaust/fuel comparisons for C5+ components. A more fundamental approach was followed in a study by the "Ricardo Oil Industry Consortium" using model fuels and developing fuels/exhaust gas composition relationships [5]. An example of this is given in Fig. 7 for toluene, isooctane and diisobutylene as model gasolines. Both pre- and post-catalyst data on HC speciation profiles are given (by group though individual species can be treated) for engine tests at a variety of steady state engine conditions. Again, the extremely different fuels produce comparable amounts of total HC emissions but their nature is determined by the type of fuel. When toluene

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23

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HC Specification of Exhaust Gas

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Figure 5. Molecular composition of exhaust gas versus fuel.

is used as a fuel, unburned hydrocarbons (i.e. toluene itself) predominate whereas the aliphatic fuels (both paraffinic and olefinic) produce significant amounts of lighter olefinic products as a result of cracking reactions. It may be concluded that, depending on the (major) fuel components, the exhaust catalyst is exposed to a different HC compound and may require different characteristics. In our opinion, this concept of tuning fuel and catalyst for maximum HC conversion is relevant to arrive at further emission abatement.

4. GASOLINE PRODUCTION---MTBE MANUFACTURE Gasoline is a complex mixture of over 200 hydrocarbons and possibly oxygenates. The gasoline pool in a refinery is made up of a number of process streams with a variety of properties. Gasoline from the fluid catalytic cracking (FCC) unit and the catalytic reformer are the largest contributors followed by alkylate, butanes and (C5, C6) paraffin and isomerate. Changing the overall composition of the gasoline pool may require major adaptation of the refinery lay out. Taking MTBE as an example (see section 2) we note that for the USA in the coming years a doubling of the MTBE content of the total gasoline pool is expected as a result of the oxygen mandate for reformulated gasoline. In considering the manufacture of MTBE a number of important issues will be dealt with, such as the requirement for new process options and the energy intensity of the processes applied. First we consider briefly the manufacture of ethers from iso-olefins and alcohols (Fig. 8). MTBE is made by the commercially widely applied etherification of isobutene with methanol, using acidic ion exchange resin catalysts. In general, methanol is made from natural gas via synthesis gas and is readily available. Clearly, expansion of the MTBE manufacturing capacity calls for more isobutene feedstock.

24

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Figure 6. C5+ hydrocarbons; exhaust gas versus fuel.

In Fig. 9 we sketch two process routes to isobutene. Starting from n-butane, isomerisation to isobutane is followed by dehydrogenation to isobutene. Both process steps have been widely operated commercially. The second step involves a capital intensive dehydrogenation reaction. Because of the intensity large plants are called for (economy of scale). An alternative and in principle less capital-intensive route is the skeletal isomerisation of n-butenes to isobutene. Previously this was not economically attractive because of the limited lifetime of the catalyst and the limited yield of isobutene. The latter drawbacks were due to the high temperatures applied previously (>400~ and the related fast coke formation.

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I

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::::::::::::

::::::::::::: ........ ..:::.:::.:.:.-

1,000

:::::::::::::

%::::::::::>, ......... ........ ~...,.,......., -,:.:.:.:.:.:.~r--"l

-CAT

+CAT TOLUENE

(b)

3,500

ISOOCTANE

I---'7

-CAT

+ CAT

DIISOBUTYLENE

iiiiii!i

::::::. :.:.:.

i

2,500 2,000 1,500 1,000

+ CAT

II

3,000

13_ 13..

- CAT

.

AROMATI CS

ii!i!i.

-~

ALKYNES

~

ALKENES

~

ALKANES

.

iii!iillii~iii

500 ..... . . . . ~

0

TOLUENE

ISOOCTANE

DIISOBUTYLENE

Figure 7. Pre- and post-catalyst hydrocarbon type emissions for model gasolines and different steady-state engine conditions. (a) 2400 rev/min, part. load; (b) 4000 rev/min, wide open throttle.

lsob, ute.ne Isobutene

Isopentene

.

+

Methanol

+,

Ethanol

+

Methanol

~

MTBE ETBE

~

TAME

Figure 8. Manufacture of ethers from iso-olefins and alcohols.

Research at the Shell laboratories has focused on the use of shape-selective zeolites, notably ferrierite (FER), for the latter conversion. The data in Fig. 10 show that at temperatures as low as 350 C the maximum isobutene yield (thermodynamics) can be achieved.

26

n-BUTENE

n-BUTANE

C- C=C--C

C-G -C -C uoP BUTAMER BP C4 ISOM

ISOMERIZATION

ISOMERIZATION

PREVIOUSLY NOT COMMERCIALLY ATTRACTIVE ~

SNAMPROGETTI UOP OLEFLEX AIR P R O D U C T S CATOFIN PHILIPS STAR

C I C-C-C

T C I

r

DEHYDROGENATION

iso-BUTANE

C - C =C iso-BUTENE

MTBE

ETB[

Figure 9. Routes to isobutene for the manufacture of ethers. iso-Butene/total-Butene

RATIO (~

80

Thermodynamic

equilibrium

(50

40

9

Experiment

20

0

100

i

I 9 200

.w

t

I 300 Temperature

t .

I 400

i 500

(~

Figure 10. Skeletal isomerisation of n-butenes; effect of temperature (catalyst: ferrierite, feedstock: 1butene). Comparison with other molecular sieves (Fig. 11) shows that the yields obtained with F E R are very high indeed. As elaborated upon elsewhere [6-8], we have proposed that the isomerisation involves a bi-molecular mechanism in which e.g. di-methylhexene isomers crack selectively to isobutene and n-butene (Fig. 12). The mono-molecular mechanism requires the energetically unfavourable primary carbenium ions. Molecular modelling [7] has provided support for this mechanism in that the branched octenes can be formed in the intra-crystalline voids of F E R but their diffusion out of the pores is hindered.

27

ISO-C4 =YIELDS (~

I

,-.

I

,/'E'"',

501"

40

,,/'""

i "~

"~ ~ ,,, ,,,

,,

30

THERMOEQ 350 ~

,,,

//

20

",,

/,/

i0 i Ok"" 0

,,,

,-""

10

~

20

~',

MFI

-

30

40

50 n-BUTENE

~ 60 70 CONVERSION (~

80

90

100

Figure 11. Skeletal isomerisation of n-butenes; effect of molecular sieves. C=C-C-C

DOUBLE BOND ISOMERISATION

C-C=C-C

I-

-'I

FER

FER ',

C-C-C-C + DIM ERISAT O NI j ~

~ ~

i

,, 1|

,,

" ~ 1 ~ ~

i t o

C I

CC I I

-- C-C-C-C-C-C-C +

l I

C

E

I

I

t

,,

,

FER

I

C

C I

C

PRIM

+ C-C-C I

CARBENIUMION

I

+

CRA~

C-C-C

+ H "/'~'{L,

SKELETAL l ISOMERISATION

c-c-c-c-c-c

+

L ...........................

CATION

SKELETAL ISOMERISATION

C

c-c-c-c-c

CYCLOPROPYL

C-C-C-C-C-C +

_j/ ",

C

I

ii

,

1

FER I t

I

C I

C-C=C

Figure 12. Proposed mechanism for the isomerisation of n-butenes.

For refinery applications the excellent stability of FER is important for the isomerisation of butenes (Fig. 13). The refinery or chemical complex process line-up to utilize the new isomerisation technology as shown in Fig. 14 involves a selective hydrogenation unit (to

28 s o - C 4 =Yield ( % w o f )

~.

I

0

I

100

I

200

~- ~tI1D_o.~

I

300 400 TIME ON STREAM (h)

~

I

500

600

Catalyst: FER Feed = 1-butane

Figure 13. Yield and stability of optimised ferrierite for the isomerisation of 1-butene to isobutene.

FCC or STEAM CRACKER

C4 or C5 --~

SHU

l--

,so.

ET.

R

A.K

MTBE or TAME

C4/ ALK

~

~ ~ , - ~ ~

Figure 14. Possible process line up in a refinery or chemical complex including the isomerisation of C4/C5 olefins. remove traces of dienes) and an etherification plant. The unconverted olefins from the latter are either recycled to the isomerisation reactor or are used in e.g. an alkylation process. The isomerisation process has been further developed by Lyondell/CD Tech and has been demonstrated at a scale of 3000 barrels per day. A further enhancement of isobutene yields can be achieved in the refinery by adding the zeolite ZSM-5 to the FCC catalyst inventory. The ZSM-5 addition leads to secondary cracking of aliphatics in the gasoline range to lower olefins. From the extreme example [9] summarized in Table III it appears that the butenes yield can be doubled in this way. All the routes to MTBE mentioned so far as well as others have contributed to the 1993 world capacity of 20 Mt/a (Fig. 15). Although this may seem impressive, the amount is modest in view of the world 1993 gasoline demand of 800 Mt/a. A full reformulation of the gasoline pool worldwide with for instance 15% MTBE would require a production of 120 Mt/a, which is 6 times the current capacity. Severe feedstock shortages (butanes, butenes) would occur should such huge amounts of MTBE be mandatory. Finally, we comment from a wider perspective on the energy efficiency of producing MTBE. In the route of producing MTBE from field butanes and methanol, a typical figure

29 Table III FCC product yields

Riser temperature, ~ ZSM-5 additive, % inventory Conversion, %vol Yields, %vol Propane Propene Butanes Butenes Gasoline

Base case

Maximum light olefins

523 0 79

549 20 89

3.2 7.9 7.8 8.8 55.9

4.3 22.0 9.8 18.6 47.1

MilHon t o n s / y e a r

AFRICA

EASTERN EUROPE

OCEANIA 30

,~ MIDDLE EAST

20

NORTH AMERli3A

O 1980

,

,,

.. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1985

I. 1990

Year

.

.

.

1995

2000

Figure 15. Projected growth of the MTBE capacity by region (source: SRI International).

for the energy consumption of the process steps involved (cf. Fig. 9) amounts to 5 GJ per tonne of MTBE produced. As the thermal efficiency of producing methanol from natural gas by modern technology is 67% (basis lower heating value) it can be calculated in a straightforward manner that the overall thermal efficiency for the production of MTBE from natural gas and butanes is 80% (see data in Table IV). Note that the route to MTBE from refinery butenes undoubtedly will be more efficient than that based on butanes since the processes involved are less energy intensive. Anyway, the direct use of butanes (as LPG) or methane (CNG) in the transport sector is much more efficient than their use after conversion to MTBE. Furthermore, refining oil to produce a variety of products (mainly LPG, gasoline, kerosine, gas oil and fuel oil) is a very efficient operation, with thermal efficiencies of typically 90% when an FCC unit is part of that refinery

30 Table IV Thermal efficiencies of energy conversion processes Operation/product

Efficiency (% LHV of feedstock)

Oil refining * MTBE ** Methanol ***

90 80 67

LHV = lower heating value. * Refinery including FCC unit. ** From butanes and natural gas (via methanol). * * * From natural gas.

(Table IV). Of course, the latter comparison is a gross simplification since oil refining gives rise to a product mix whereas MTBE is a high-octane quality gasoline component. A more comprehensive study (so-called "well-to-wheel") comparing gasoline components proper indicates that the use of MTBE is attractive from an overall CO2 emission point of view (relative to high-octane oil-derived components). The latter observation is due to the hydrogen rich raw materials used (methane and butanes) rather than the energy efficiency of the processes involved. We therefore conclude that direct use or modest refining of energy carriers is more efficient than their extensive conversion to "synthetic" gasoline components such as MTBE.

5. ALTERNATIVE

FUELS

Summarising what has been discussed in section 4, we present the global production of some alternatives in Table V. The scale of demand for gasoline calls for huge investment to replace gasoline by, e.g., methanol. Economic factors as well as the low efficiency of methanol production (Table IV) indicate that careful consideration is required before vigorously pursuing alternatives like these. A global perspective of the use of alternatives in the transport sector is provided in Fig. 16. L P G and C N G are used to some extent. Special circumstances (Brazil - - ethanol; South Africa - - gasoline from coal) have led to larger contributions in some parts of the world.

Table V Manufacture of (alternative) gasoline components- World, 1993 Component/product

Amount (Mt/a)

Motor gasoline, total MTBE Methanol (Hydrogen

800 20 20 40)

31

l*/.fuel

~

"

I

~

,-..

F'~

~%'t

"1

LPG

E~)hafn?ell

~" 1~ ~' .l

-q

~ ~ 1 ~

y elc gasoline 40%fuel

Fuel and vehicle percentages are aproximate.

~'~~'

~ ~

~ CNG/LPG 4%fuel

..~ ,~" / " /

4 % of vehicles

Figure 16. Main users of alternative fuels in the transport sector. 6. CONCLUSIONS Significant reductions of emissions from gasoline-fueled cars have been achieved by introduction of the exhaust catalyst in combination with unleaded gasoline. The effects of gasoline properties and composition on regulated emissions (HC, CO and NOx) are complex and there are large variations in sensitivity between vehicles. Much work has been done, but there is a clear need for further work in Europe, especially on sulfur effects and aromatics/distillation. This will be covered in the new E P E F E programme. - The molecular composition of the exhaust hydrocarbon species closely reflects the fuel composition for C5+ compounds, whereas lower hydrocarbons in the exhaust gas are mainly combustion products of fuel aliphatics. One of the most "refractory" hydrocarbons present in the exhaust gas is methane thus presenting a challenge to the exhaust catalyst developers. - A more comprehensive study (so-called "well-to-wheel") is required to properly indicate the attractiveness of the use of MTBE from a CO2 and energy point of view, addressing both local and global environmental aspects. - MTBE manufacture from FCC-produced butenes can at least be doubled by skeletal isomerisation of normal butenes to isobutene. Addition of ZSM-5 to the FCC catalyst inventory may be applied to quadruple the MTBE output. -

-

-

R

E

F

E

R

E

N

C

E

S

1. A.K. Rhodes, Oil & Gas Journal, January 17th, 1994, p. 16-20. 2. G.J. den Otter, R.E. Malpas and T.D.B. Morgan, SAE 930372.

32 3. 4. 5. 6.

T.D.B. Morgan, G.J. den Otter, W.W. Lange, J. Doyon, J.R. Barnes and T. Yamashita, SAE 932678. E Beckwith, EJ. Bennett, C.L. Goodfellow, R.J. Brisley and A. Wilkins, SAE 940310. P.R. Shore, D.T. Humpries and O. Hadded, SAE 930373. H.H. Mooiweer et al., paper presented at the 1st European Congress on Catalysis, Montpellier, September 1993. 7. H.H. Mooiweer et al., paper presented at the 10th Int. Zeolite Conference, Garmisch-Partenkirchen, July 17-22, 1994. 8. J.E. Naber, K.E de Jong, WH.J. Stork, H.P.C.E. Kuipers and M.F.M. Post, paper presented at the 10th Int. Zeolite Conference, Garmisch-Partenkirchen, July 17-22, 1994. 9. T.E. Johnson and A.A. Davidan, paper presented at the 1993 NPRA Annual Meeting, San Antonio, March 21-23, 1993.

A. Frennet and J.-M. Bastin (Eds.) Catalysis and Automotive Pollution Control III Studies in Surface Science and Catalysis, Vol. 96 9 1995 Elsevier Science B.V. All rights reserved.

INTERNAL

33

COMBUSTION ENGINES PROBABLE EVOLUTIONS AND TRENDS

P. E y z a t

ENSPM- Director for Combustion Engines and Hydrocarbon Utilisations

1. I N T R O D U C T I O N

The first time I participate with a group of specialists, to forecast the type of converter to be used in the coming years was in 1964. The S.A.E. entitled the session "Should we have a new engine ?". By itself, the question mark indicates how confident the organiser was for the possible quality of the reply. Naturally, we have been more often wrong than right. The mistakes classicaly are made of over optimistics evaluations of new contenders and over pessimistic ones for the adjustment potential of the standard engines. Having this lesson in mind, I forecast that the present "4 stroke-fuel" ticket will maintain its leadership for at least a decade. This is to say that the market for the electric car use will be limited to certain over populated area, where a consensus will be agreed on the extra-cost sharing between citizens and vehicle users for the sake of local pollution abatement. Another big consequence of this hypothesis is that the thermal engine will still have to be adjusted and judged in city conditions : low speed, low torque, short trip. Secondly substitute fuels, biomass or others will have to adjust to basic standard engines or to limit their use to dedicated local fleets. As will be seen later on, the 4 stroke-fuel ticket might be very different from the present average : a lot of imaovations are in sight. In sight, is by no means, equivalent to predictable : who would have, 15 years ago, forecast the huge discrepancies between developped countries on the diesel share market ? 2

STROKE SPARK-IGNITION ENGINES

2.1. Standard systems The most common engines use a lot of fixed system which might well

34 become variable and adjusted more and more often. Let us particularly look at 9 Connection pipes : inlet and exhaust 9 Valves lift, number and profile 9 Compression and expension ratio 9 Supercharging All these characteristics, whenever constant, result from very accute balancing and compromise. Naturally low cost is the goal pursued by technicians. Sometimes the market allows some more degree of freedom in some niche : fixed items become variable ones. If users are satisfied, and if extracost becomes manageable for a bigger production line, then the solution is extended. Japanese firms are often in the front line for engine modifications, naturally not all of them are destined to spread and become a world standard. The other big problem created by an item which is modified from stable and fixed to variable is the real time control of this system. You need a CPU, pick-up sensors, actuators. You must define a strategy, create hysteresis, when not natural, in order to avoid instability. Furthermore you must never forget that the engine behavior is mainly transcient. The time constant of interest ranges from tenths of milliseconds, (noise and vibrations) to milliseconds, (cycle to cycle variation) and seconds or even minutes. The average trip is so short (1 or 3 km) that when you stop your car neither the water nor the oil are at their equilibrium temperature. When you remember that oil viscosity plays a major role in engine friction and is very sensitive to temperature (you need a log-log scale to draw a straight line for viscosity versus temperature law). You realise how difficult it must be to define a strategy and to check it.

2.2. Inlet Pipe adjustment Already performance car use inlet pipe of variable accoustic lengths. A well localised butterfly can be automatically actuated, offering two and sometimes three different design lengths. The origin of the variation of the maximum mass of air trapped inside a cylinder, a quantity directly colmected to the torque, is easy to understand. Imagine a pipe closed at 1 by a valve and colmected to the atmosphere at 0 (fig.l). If you create a brief suction at 1 you will observe your 2L pipe oscillate in quarter wave, e.g. after a time equal to + ~ , with C the sound C speed, you will have a pressure increase at your valve. Naturally, if you close 2L your valve around to + -C you will benefit from an increase of air filling. But

35 later at to + 4____LLit will be the reverse, you will empty your cylinder. So at high C nmning conditions, you need a short pipe and at low nmning conditions a long !

0

_2__L

_LL.

C

C

I

L/

Fig. 1 Wavepropagation pipe. Naturally the real phenomenon is for more comple. There is a volume effect, (Helmotz resonator) friction losses at the boundary layer, and losses due to curvature radius of pipes and to abrupt change of surface. Admission can also be thermally heated" in accordance to a thermal sensor you can heat up inlet gas during cold starting by ensuring a heat transfer from the exhaust gases. Or create an electrically heated plate in order to compensate for the latent heat of vaporisation of the fuel. The cooling potential of this effect can be very significant 9about 30 K for gasoline but more than 200 K with methanol. Hysteresis effects are described in the (fig.2). S

rq

,

-

_

V

N0"

NO

blo*

Fig.2 Hysteresis Tigger

N

36 If you decide that you will change your configuration for a given value of a parameter, e.g. running condition No, and you try to stabilize at this point, any perturbation, however small, will make the system oscillate between state 1 and state 2. To avoid this phenomenon, you define two values : one, let us say No + is selected when N is going up and on the way back you change at No- which is lower than No + In the same circumstances, you can have two different equilibrium conditions, you create a bias in test reproducibility.

2.3. Exhaust pipe adjustment The waves behave in the exhaust as they do in the inlet. They are only travelling at higher speeds due to exhaust temperatures. So you can also imagine a variable exhaust pipe which creates a depression at exhaust valve closure, if you want to increase the torque, and an overpressure, if you want to increase the internal exhaust gas recirculation very efficient means for NOx abatement. However the cost of an exhaust butterfly is much higher than its inlet equivalent and they will probably be reserved for E.G.R. and may be for prompt E.G.R., an interesting idea which is described in the (fig.3). {r~mC}

/2000

9OOO

o

e~we~/

mxnaust vslve ctosm

Fig3 Prompt E.G.R.:Recycling the last part of the exhaust If you analyse the concentration of unburned HC in an exhaust burst, you will find that the instantaneous value can be far higher than the average ones. Particularly at the end of the exhaust, at a time when the piston has scraped all the boundery layers, you see a pulse of high HC concentration. If you imagine this part of the exhaust being recycled then you will be more efficient : you will obtain the normal effect on NOx you are looking for and you will give HC a

37 second chance to burn. In some cases, you can recycle 3 5 % of the HC with only 10 % E.G.R. 2.4. Cam profiles and number It is obvious that at high nmning conditions the filling of the cylinder will be limited by the surface offered by the inlet valve when open. One of the biggest technological innovations for SI engines has been the 4 valve-per-cylinder concept. However at low running conditions, too high a surface, means lower gas speed and consequently smaller pressure wave amplitudes in the inlet duct. The 1 suction phase of (fig.2) is smaller in accordance with p+~pV2= cte , and the

2L later is smaller even for a well tuned inlet pipe. C It might be of interest to have a variable number of valves according to the running conditions. The possibility of modifying the cam lift profile can be fruitfully utilized for combustion speed adjustment. The combustion, expressed in percent bumed per crank-angle rotation of the engine diminishes with an increase in both gas dilution (air excess or E.G.R.) or running conditions. To improve your combustion speed, when it is needed, you must increase the turbulence in your combustion chamber. One way of doing this is to vary the tumble (an air rotation whose axis is parallel to the shaft) versus the swirl (an air motion of perpendicular axis). The creation of turbulence near top dead center (TDC) where you need it, comes from the tumble which is destroyed when the piston comes close to the head. So you can specialize your valves for tumble and swirl, and by adjusting their lift with the conditions you will correct the otherwise detrimental evolution of combustion speed. Finally, if you add the gas dynamic effect which, in COlmection with pipe length, explains why you must open your inlet valve earlier in the cycle and close it later at high running conditions than at low running conditions. You can imagine easily how fruitfull an adjustable cam mechanism can be. Some examples of cam mechanism adjustment and uses will be briefly described now. gain of pressure at At -

2.4.1 Mechanical systems The Mitsubishi system uses two cams, one for low the other for high speed range. Cams are driven, or not driven, according to the position of a hydraulic piston (fig.4). Here you Call have three situations. At low torque and low running conditions (fig.5) two cylinders are discolmected (their valves remain closed).

38 In such circumstances a gain in efficiency mainly from the reduction of pumping losses, is obtained. Apart from this case, one or other of the cams is driven. The Honda system is of the same type.

[Low-speed and hioh-speed c a m

profilesl

High-speed

Valve I i ft

Low-speed

I Lar~e~ lis ~ m e a n s valve open

I /~/ I - - ~ /s"

" longer

9

"'\

;%

I

n 80C

TOC Crank

80C

angle

Fig.4 Variable valve Timing

I

" _.i!,V /

, d ",,&,,l/

I

0

i

EnqLne

Fig.50peratingranges

I

I

I

2 spee4

(,

3 to00

rpm)

/

/

!" ,""/" ,"

I

~

I

5

1

6

l

7

8

39 2.4.2 Continuously adjusting system The potential of hydraulic and electronic control can be pushed a little bit ft~her. Siemens (fig.6) for example uses a solenoYd to control the oil pressure in an actuator located between cam and valve. CAM

VALVE

-'

Lr~-~

Valve Lift 3

Crank Angle

(High = Open) ~f

Solenoid Waveform

J5

7---,6

Fig.6 Siemens variable valve actuation Considerable development work is being done to electronically govern very high injection systems for Diesel engines. Such a system might easily be used for valve motion. It offers a fully flexible and continuous lift profile adjustment, but its cost remains too high at present.

40 2.5. Lean burn concept Lean bum is a very old topic in engine research. The basics are well understood. Gains come mainly from pumping losses, which are those of the Diesel engine, and from thermodynamic advantages linked to the more favorable Cp/Cv ratio of air compared to a stoechiometric mixture.

2.5.1 Stratification A stoichiometric or rich mixture near the spark plug ; air in excess close to the botmdaries is one way of solving the problem (Baudry process, Texaco, Proco are well known examples). Besides fleet applications for Texaco, these solutions have not been able to fulfill industrial requirements. Problems arose from high pressure gasoline injection, reproducibility and wear, (a lot of progress has recently been reported in this area) and the quasi perfection of combustion needed. In fact for very lean mixtures the exhaust temperature is low enough to make oxidation catalysts inefficient. Then the unburned HC created by gas-gas coinching inside the cylinder may be far above legal treshold limits. 2.5.2 Homogeneous lean burn engines The goal is no longer to have an unthrotlled engine but to bum a nearly homogeneous mixture, at a point where NOx emissions are compatible with legislation, at least until NOx catalytic systems working in lean conditions and fulfilling automotive requirements are available. A famous example is the Honda VTEC-E engine (fig.7) Another type is the Mitsubishi (fig.8) which is a compromise between purely stratified charge engines and homogeneous lean bum. The Honda engines clearly demonstrate that the ambition of this manufacturer to create a"Diesel Killer" e.g. an engine emitting less CO2 than their best Diesel competitor is not out of reach (fig.9). However, with the breakthrough created for the sake of the two stroke engines in gasoline direct injection, notably by Siemens, or with air injection, (orbital or IAPAC) the 4 stroke lean bum engine is clearly a potential wi~mer for tomorrow's green house engines. Already existing results evidence this forecast. 2.5.3 Heavy_ EGR engines Instead of diluting by air you can think of diluting by burned gases. From a thermal stand point lowering burned gas temperatures can be equally attained by oxygen excess or CO2 excess. Drawbacks are linked to CO2 dissociation at high temperature, an obviously endothennic evolution, and kinetic effects. A comparison of both solutions is given in (fig.10). This clearly shows that an optimized piloted E.G.P. can offer a drastic reduction of NOx (this solution is

41

10 --E

8

-J

4

~

2.

o

Exhaust I

-IaO (six::)

o

Sca,',aa,rd

,'-S

i!

,,/. /

"~",

_

,.

E=ginc

I

.

:or:

ores

( Si=gle-;x~rc ;"j=.~Jo,',

!

g~

S[amese pot:

Double-porz

'

croci Crank Angle (degree)

Fig. 7 Honda lean burn VTEC-E ~C~."

Intake - Pr;rnaryVaNe \

m.~ec'..io=

I

Fig.8 Mitsubishi Vertical Vortex Lean burn engine

'

1BO

(BEXZ)

42 Turbo D.I. 1.9 liter

Specific fuel consurnpr,on (g/k~'Vhl

:~i

II

(bar)

~ -"

i

~_~l~o~~

d,

'

- " ~

~.

'

...

.~_ 2"J

2 I~ ' ' 35o OI',,~A-------&'500

~ i i"i

~-4 [ 1 1 1I 1000

i I J

2000

3000

Type

RPM

PME

C~iine Lean Bum

1500

1

Point

4000

CS

(~kw.) 490

Fig.9 Honda MTEC-E m a Diesel map 20-

~

5

.....

330

":f

1.00

;

l .......

0-90

~o

0.80 Equivalence r'at'J o

~'o

E.G.R.

0.70

.,

0.60

1

30

2o

rate

Fig. 10 Lean burn versus E.G.R. 2000 rpm IMEP 4 bar

43 compatible with 3-way catalytic requirements) even if C02 optimization remains in favor of air dilution.

2.6. Compressionratio 2.6.1 Mechanical adjustment Changing the shait to head distance is not easy the system must sustain heavy forces and adjusting time must be low to follow the ear transcient. In spite of these difficulties researchs is pursued" potential gains at part lead justify sustained effort in this direction (fig. 11). thermal engine efficiency

~o

~

%

,,,,,.... . . . . . . . . . . . . . . . .

....

~ . . . .

~..~-- /

, ~ ,.

so

~~..-~'-"

--

vanable compression and variable valve timino

. ........ ! ---.T.~..L..:-..,~."

I

variaDle comDresslon with throttle control

,

60

,

,,.,,,,

,

[

I

-'~_t"~"~-.~_..~~

]J .

/ (,,,'9)

alve timing

30

0

throttle control I 9 20 40 60 normalized load

RPM ..- const. i 80

%

100

Fig. 11 Variable compression ratio engine. Theoretical gains(VW) 2.6.2 Cam profile adjustmen.t The work done by gases occurs during the expansion stroke. Mechanical systems used today make compression equal to the expansion stroke. It is possible to avoid this combination by using a special cam profile adjustment along with the well known Miler principle. If, during the first part of the upward movement of the piston you maintain the admission valve open, you are in fact reducing the compression stroke. Mazda is said to be marketing such a solution soon (fig. 12).

2.7. Enginecontrol

Closed loop control used to maintain the fuel/air ratio within narrow limits is well kaaown. A lambda sensor delivers a very sensitive signal to oxygen concentration around the stoechiometrie ratio. This signal is used to pilot the injection in order to correct observed deviations. Besides limitations coming from trine constants, (those of the lambda sensor and the injection system) the liquid gasoline film deposited in front of the inlet

44

,

"~\~

\,

.

,..'

,

P ~ c e s z of M - M i l l e r c y c l e e n g i n e Coo~ ~ ' ~

l~

im=m ~

~',mtger ztKI It,,-

6 oPett.

m~m ~aL P'nm~m

Imam vlP,nl

~

~

ffa= t=zzl~"~ure= am ~w~'

!

==,.on==,=

------------- I l t i l

COIplOa

tl~t~

~n==r

"iJ ~

llllllthlll

~p/oll

i

~

' F..,cMom" - - "

Fig 12 V6 Mazda

20

t

'~I

-

"I

~"

io.,\

A

vo

5 0

2

4

lime(s)

6

8

10

o~l "0

J

/~

2

.

.

4

/,'~

\

, .

i

.

.

time(s)

.

6

8

6

8

~'

I

10

0.3 0.25

2

0.2

1.5

~o o.15

"~E 0.1 Q

o.os

-

~ ,

.;

oo

time(s)

2

4

lime(s)

10

Fig. 13 simulation of a simple closed lopp control(E.N.S.P.M.simulator)

45 valve can seriously alter the accuracy of the control in transcient conditions. Part of the fuel injected is condensed on the pipe wall. This film evaporates and due to the high air turbulence intensity, secondary droplets are also created. Then a given cycle is fed with part of the injected qumatity and with part of the fuel film ~ a phenomena completely outside the simple closed loop control l o g i c s . A simulator of the car and engine system has been developed and placed on a work station at ENSPM. It will help us to understand the strange behavior of an engine with a simple control system. Imagine you force (fig. 13) the throttle to follow the law described in A. The instantaneous equivalence ratio will follow the curve drawn in B. The drop of 40 % which occurs in the first second is well known (air delay is smaller than injection delay). The very wide oscillation occuring between 6 and 9 s deserves some comments. At the begilming of the throttle opening rich mixture is measured by the lambda sensor. Naturally (C) the injection duration is adjusted. But even with a smaller injection duration the film continues to fill the cylinder (D). Then the C.P.U. interprets such behavior by continually reducing the injection duration. Just before 7 seconds, the injection has been halted and the equivalence ratio remain rich ! This lasts until the the liquid film disappears (D). As is shown in (B) the cycle by cycle equivalence ratio oscillates between .3 and 1.4. This is why the control system must be corrected for transcients. One way most often used today is to enter empirical laws in the C.P.U. Another way is to model the non linear fuel film system and to enter it in the C.P.U. of the engine : besides lower emissions, a more stable engine rumfing is obtained (fig.14). Obviously the direct injection S.I. engine definitely solves the fuel film trouble. As has been said earlier, on the lean bum engines, teclmological limitations of high injection pressure gasoline systems have now been mostly overcome. For those involved in the development of catalytic muflers the problem of engine control is of the upmost importance. Bearing in mind what happens with simple engines, one can easily imagine what problems can arise in the transcients of an engine in which duct length, cam profile and compression ratio are adjusted through non linear algorithms stored in the C.P.U. Lastly, optimisation will also have to include the exhaust pipe and its catalytic bed which add its own transcients : oxygen storage, thermal inertia, pressure drop...Comparing two catalytic systems at a ULEV level might not be possible without perfect knowledge of the C.P.U. program.

46

~vntm! w,U.. Ssc.A~v S~tr

S p r c d l ' ~ a t T SuJte~,T,

17 w

17" o

,, 5

to

" lo

!$

~c

17 .

.

' t

t6~

.

9~.

.

.

........

t ........

_ 3s

3o

.

............

:.or- . . . . . .

z~

(s)

I ]

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.

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.

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.

.

.

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.

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35

I

12 L

o

I c

to

I$

20

umr

ar

7.5

(s)

.~ ......................................."..............i............. ".................... ] J

,-

141

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w_,.,..~,,..,.,.....__.r~._..,_.

5

io

iS

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]

......................................................................................

~

~o

-~5

Fig.14 (From Ricardo ISATA 93EN032)

Germany Italy Spain U.K. France Europe(17 countries)

1990 10,8 7,3 14,7 6,4 33,0 14,1

Fig. 15 European Diesel market share

% o f total car 1991 1992 11,8 14,8 5,7 7,6 12,7 16,6 8,7 12,5 38,4 39,0 14,6 17,0

1993 15 10 21 17 44 19-21

47 3. DIESEL ENGINES

The Diesel engine share of the automotive market has strongly increased in Europe during the last few years (fig.15). Peculiar drawbacks of this type of engine are well knowal : noise, particulates and NOx. Diesel engine specialists have made impressive progress in the last decade on the noise side. In front of catalyst specialists I will not comment further on particulate filter regeneration and NOx reduction in lean conditions ; these are two topics of research in your field. I will just remind you that diesel specialists will have a sigh of relief if you can offer them an industrial catalyst solution ! Contrary to their S.I. competitor, progression Diesel engines is not easily identified from outside by non specialists. Their teclmological breakthroughs appear mainly in clearance, reproducibility, machining precision. A bad engine is not very different from a good engine. Basic solutions for tomorrow are already on the market : prechamber of the Ricardo or Mercedes type, and direct injection engines (fig. 16). \

;I

l

Direct Iniection

Swirl Chamber

Fig. 16 Diesel combustion chambers

Recent progress in prechmnber engines (I.D.I.) has come from the prechamber detailed optimization (localisation of the glow plug, maintained in action after the engine starts during an adjusted time, flow guidance at the outlet of the prechamber into the piston). Electronic control of the injection system can, and probably will be developped in future engines. Regardhlg the D.I. engines, noise reduction occurs through mechanical and combustion improvements. For mechanical noise the piston slap phenomenon (a vibration created by the piston to cylinder shock when the piston travels, near T.D.C., from left to right) decreases atier better adjustment of clearance, shape

48

and weight. Combustion noise is closely connected to fuel injected during the self-ignition delay. With a given fiiel, one way of reducing the delay period is to use a small pilot injection. A teclmological break-through enables such an injection with a two-spring nozzle (fig. 17). t

9 8

7

15 4

12

3 5

IO 2

It

._.J PreLift H I I NozzLe Hol,der 8odid

2 Stoo SLeeve

3 Sorino 5eat 4 5brin9 5 Pl-essure kdjust,ng 5him 6 Sh,m

7 Spring 5eat 8 Spr ,ng

9 I0 II I2

Shim Adaoter PLate Noz'zLe @etoining Hut Pressure Pin

Fig. 17- Bosch two spring nozzle

Fig. 17 Bosch two spring nozzle A very small prelift (some htmdredths of mm) is limited by a second spring. The increase of force needed to complete the lift creates a delay. During this time the small amotmt of fuel injected during the prelift self-ignites and the main part of the fuel injected later in an already burning mixture bums less abruptly than with normal injection. If you add the fact that in order to obtain smaller droplets, injection pressure is increased (1200 bars today, 1500 to 1700 bars tomorrow) and at the same time nozzle hole diameters are reduced, you can understand where Diesel progress lies : in details, whose industrial management is the key point for competitivity. For newcomers, in the Diesel field, the question is "will it be an NOx regulation situated between what is possible for S.I. engines and what is not possible for Diesel engines ? Nothing of this kind is foreseeable in the coming years mad on the contrary the Diesel market share is increasing even in countries where there is no fiscal advantage for its use. However such a threat in an area where technological knowhow needs time to be created, acts as a brake. 4. STROKE ENGINES The more advanced contender of the standard 4-strokes for car powering deserves some COlmnents even if, as it has been assumed in the hatroduction, the

49 4-strokes has sufficient potential to remain the winner. And, furthermore, the two strokes has its own market for two and three wheeler vehicules. Reasons for two-stroke efficiency gains lie in reduction of friction losses and pumping losses at part load (fig.18). Friction losses are mainly related to cylinder capacity and running conditions : the two stroke which creates more power from the same capacity has lower friction losses. Improvement in pumping losses benefits from the fact that the S.I. four strokes functions like a vacuum pump during the suction stroke at part throttle. Gains in efficiency occur during city driving conditions : a 15 % reduction can be attained. Another potential big advantage of the two stroke is size reduction, a quality that designers appreciate even more than weight reduction for the freedom they gain in hood shaping (fig.19). To obtain these gains, engineers must have solved the fuel short circuiting which makes the standard carburetor 2 stroke a high pollutant and low efficiency enghle. In these engines, the burned gas is scavenged by the fuel air mixture which pushes it out. If we do this, part of the flesh mixture goes directly to the exhaust without having participated at all in the combustion phase. Injection offers the solution : scavenging will be done with pure air, and fuel injection occurs close to or after the exhaust port closure. Teclmological solutions are numerous and they can be examined through their injection system : Direct injection systems, mainly developed by Toyota, Chrysler, PSA and Renault to cite some of them. Key points are the high injection pressure system and the control of the fi~el air mixing which must be optimized in a very short time. 9 Air assisted injection systems. Two sub-classes must be defined : medium pressure, small amount of air, most often with an air compressor. The most famous name is ORBITAL, and a lot of licences has been taken by manufacturers. This is probably the closest to industrial car use of all solutions ; - low pressure, amount of air compressed below the piston in the crankase, typical of the IAPAC system. Air injection systems offer a finer atomization which make combustion and mixing phenomena a little easier to solve. However the lubrication of a dry crankase engine is not easy to solve with lost oil : low enough for pollution, high enough to prevent wear of moving parts. Toyota has avoided this by using a standard 4 stroke teclmology : 4 valves per

50

100

Four-Stroke

80 Percent of Indicated Power 40

Two-Stroke

lO0

i/i

Percent of L I W l l l i ~ i ~ ; ; i i ~ ; - ~ 1 7 6 Indicated t i V O l i " ~ i J Power L ~ I ~ ~,

,

'

~

'

.

~

,

-

I .

I1~~~,~;~.~1~.!

20 20

40

60

80

100

Percent of BMEP

0 - ~ 2 ( ) - -4-0 -l~O 80 Pumplng / Losses Percent ol BMEP

Fig. 18

~

Fi ENGINE SIZE C O M P A R I S O N

4 - STROKE PEUGEOT TU3 1360 cc 50,5 kw/5600 RPM - 109 raN/3000 RPM 2 - STROKE IAPAC 1230 cc 55 kw/5000 RPM - 125 mN/3000 RPM

I00

51 cylinder, normal crankase, extemal blower for exhaust gas scavenging. NOx emissions are obviously the limiting factor.

5. CONCLUSION

Petroleum based fuels will remain the main sources of energy for transportation. In the car sector, the four stroke engine has a very good chance to maintain its predominance. Electronics offers it a great potential for real time optimisation of a lot of possible adjustable technologies : cams, ducts, compression ratio, firing cylinder with E.G.R. or lean combustion are some candidates for flexibility increases. The Diesel engine will maintain its impetus and the two stroke will enter into the game if efficiency and CO2 reduction become a greater priority (fig.20).

Cycle ECE+EUDC

HC+NOx g/kin

I

I

I

I

I

I

iDiesel IDI I /. . . . . . . . .

i

I

I

Diesel DI 1,0

4 stroke lean burn

i _j

4 stroke R=I

I

0,5 i i i

0,0

i i 4 stroke~ DI

I

I

-30%

-20%

;

-10%

v

i

0

+10%

Fig.20 converters comparision However unless an NOx catalytic bed working with oxygenated exhaust gas is available, an NOx threshold may be defined which condelnns them. Even if very unlikely, such a hypothesis cannot be dismissed.

52 While these trends define the backbone of the technological evolutions, as we see it, they leave some place for niche markets. However, and we learnt this with unleaded gasoline, the idea of having a new dedicaded source of energy for a new fuel seems hopeless. A new fuel or an extension of its use will benefit from the naturally more flexible engine of tomorrow, it may be the case for L.P.G. for example. Although Natural gas suffers from the constraint of its onboard storage, its availability and CO2 bonus explain the strong political pressure for its use elsewhere. Combustion characteristics of natural gas, low combustion speed and long self-ignition delay, create an incentive for a dedicated engine. It is forecasted that starting with fleet use, the number of filling stations will increase and this will help to spread tile use of gas engine.

Model Reactions and Model Catalysts



55

LABORATORY DATA FOR THREE-WAY CATALYTIC C O N V E R T E R MODELLING D. Schweich Laboratoire de Gdnie des Procddds Catalytiques CNRS-CPE, 43 Bd du 11 Novembre, BP 2077 F-69616 Villleurbanne Cedex


Numerical simulations could be advm~tageously substituted for some expensive experiments with an engine bench. However~ the reliabili.ty of the numerical results depends on tim assumptions made and on the quality ot the physical and chemical parameters involved in the model. Presently, converter models work well for specified experimental conditions, but there is no decisive proof of their predictive ability in a wide range of. conditions (Pattas et al., 1994). This is because four importmat topics deserve further attention: Kinetics, External heat and mass transfer processes, Intemal diffi~sion in the wasl~-coat layer, Flow distribution in the monolith. The experimental and interpretation problems related to these topics are reviewed in tlae next sections. 2. Kinetic data

Converter models require reliable kinetic expressions that account for the composition and temperature dependence of the reaction rates. The temperature dependence is essential for predicting light-off performance, whereas tlae Consequences of the concentration dependence are more difficult to assess. Most models rely on the historical data provided by Voltz et al. (1973) which were obtained under oxidizing conditions on a platinum catalyst. Ttie rate expressions are of the Lmlgmuir-I-fi.nshelwood (LH) type and account for t!le infiibition clue to NO. Unfortunately, there is no mechanism supporting the expressions that should be considered as fitting rate laws. For instance, the heat of adsorption of NO has the wrong sign. The first rate expressions concerning the simultaneous oxidation of CO and reduction of NO were provided by Subramanian and Varma (1985). Here again,

56 the expressions are of the LH type, but_ they also involve fractional and positive orders which are of empirical nature. It seems tlmt there are no available rate expressions for NO reduction by hydrocarbons. _ To point out the main problems tlmt arise in kinetic investigations we will focus on tlle simple example of CO oxidation for which reliable l~inetic data are available. Using a detailed model we will generate sample "experimental" results corresponding to various experimental conditions. We will show how these results can be interpreted back with kinetic expressions, and what are tlae difficulties of this "inverse problem". However, let us mention that numerical calculations require that the rate remains bounded. This forbids negative orders in empirical rate expressions. :Strong inhibition by reactants or products must be accounted for by a Lmaglnuir-Hinshelwood type expression. 2.1. The example of CO oxidation There are many kinetic expressions for CO oxidation which are derived from realistic mechanisms. Many of them, together with the expressions from Voltz et al. (1973) and from Subramanian and Varlna (1985), reduce to: r=

kxcoxo2

(1 + Kxco)2

mole.m -3 of wash-coat.s- 1

(1)

where xi is the mole fraction of species j K and k obey van't Hoff and Arrhenius laws res~pectively. Based on Hecl~ et al. (1976) the kinetic parameters are: k 0 = 4.14 1016 m o l e . m - 3 . s -1 E a / R = 12600 K

K o - 65.5 AHad s / R = - 9 6 1 K

(2)

Ea is the apparent activation energy that is composed of the contributions of the intrinsic activation energy and of some heats of adsorption. Equations (1) and (2) were used to generate sampl, Light-Off (LO) curves corresponding to an inlet fluid containing 2% mole CO. 1% mole O2 diluted in an inert gas, and a GHSV, based on total reactor volulnel of 75000 h-l STP. The reactor is either a monolith with square chalmels of widtl: Dh = 1.1 iron, with a wash-coat thickness w = 10 mm, and a void fraction eM =.0.76, or a packed bed of crushed catalyst particles diluted by an inert solid with an intergranular void fraction eB - 0.36. The volume of catalyst particles per unit volume of intergranular gas is f = 4weM/(DheB) = 0.077. This ensures tlaat the volume of catalytic material per unit volume of reactor is identical in the monolith and in tlie packed bed (See appendix). 2.2. The light-off curve LO curves represent most laboratory data obtained with either a monolith or a fixed bed offcrushed catalyst. Figure 1 shows simulated LO curves in an adiabatic monolith where the heat and mass trmasfer processes compete with the catalytic reaction, and where heat conduction through the solid is neglected.

57 1.0

.~ O

0.8

0

+•-7/ 4" a/R IE'

=~ 0.4 06 i 0r,.) 0.2 0.0

-

"18500K

1.0 O

"~o 0.8 I - ~ 0.6O 0.40 0.2-

44"

E'a/R = 12100 K]

0.0 I I I I I I ' I ' I ' 560 580 600 620 640 600 700 800 T gas inlet (K) T gas outlet (K) Figure 1: Light-off curve (crosses) versus inlet and outlet gas temperature. Fitting (dotted curve) the leading part o f [he curve yields an apparent activation energy. Simulation of an adiabatic monofiih, no axial heat conduction.

Usually, one draws the curve versus the inlet gas temperature. At low temperature the reaction rate is proportional to the conversion, and one may qbtain an apparent activation energy, E'a, from an Arrhenius plot. Remark tirst that equations (1) and (2) imply tlmt: 12600 K < E'a/R < 14500 K (3) according to whether the reaction is strongly inhibited by CO or not. Figure 1 shows that the estimated E'a are not in the required interval. More generalIy, the LO curve gives ml overestimate of E'a, when plotted versus t-he inlet gas temperature. Consequently, the leading part ot the-LO curve for a monolith Iias no simple kinetic interpretation. . The bias is essentially due to the .progressive temperature increase along tlae catalyst bed tlmt accelerates tlae reaction: The inlet temperature underestimates tlae average catalyst temperature, and using tiffs temperature to determine E'a yields an overestimate. Conversely, the outlet temperature overestimates the average temperature, and E'a is then underestimated. 2.3. Presence of an adsorbed and non reacting species

The presence of an adsorbed species is also responsible for misleading results. Figure 2 illustrates the effect o f a constant trace amount of an adsorbable inert species that increases the light-off temperature (TLO) by 35 K. Mabillon et al. (1994) gave an evenmore convincing example. They showed that acetylene preadsorptlon can shift the LO curve by 100 K. After light-off, acetylene bums, and a second experience, without acetylene preadsorption, yields a lower TLO. In both cases, the LO curve shifts because catalytic sites are occupied by strongly adsorbed species that i~flfibit the reaction. According to LH theo.ry, the inhibaion is essentially governed by the adsorption characteristics at equilibrium without reaction. Consequently, adsorption isotherms under non reacting condition must be measured. Tliey yield the adsorption constants involved in a LH rate expression.

58

~1~ i,o f . . f K]

.o 0.8

0.6

= 591 K I [TLo= 627

o o.4 _

_

or j 0.2 0.0-

j

I

560

I

580

2.4. Presence

i

600 620 T (K)

of other reacting

i

640

Figure 2: Light-off curves for CO alone (Continuous curve) and CO plus a strongly. adsorbed inert species (dotted curve). Simulation Of an adiabatic monolith.

species

One often performs LO experiments with a mixture of more than two reacting species, :for example CO, 02, and a hydrocarbon. On a.Pt-Rh-CeOT. catalyst, 1/ydr0carbon LO thkes place when CO ~s almost completely converted. For a given inlet temperature, the gas and solid phase temperatures are thus much higher in the presence titan witlmut CO in the feed. This implies tlmt the hydrocarbon TLO measured by the inlet temperaturejs higher in the absence tla.an in the presence of CO. Consequently, the light-ott temperatures for multiple reactions are teclmical data tlmt have no fimdamental interpretation. Kinetic studies must be performed with simple mixtures. 2.5. Heat and mass transfer

One of the drawbacks of the monolith is the heat and mass transfer resistance between the bulk gas phase and the wash-coat. This resistance can be lessened when using a fixed bed packed with crushed catalyst. Figure.3 illustrates the LO curves when the heat and mass transter processes are not the rate determining steps. Two cases are considered depending on the efficiency of heat removal from the catalytic bed. Either the effimency ~s low and the bed.is close to adiabatic condition, or the efficiency is high and all the phases are at the temperature of the inlet gas. _.l

1.0--

.o 0 8 -

.o 0.8E =18700 K g 0.6. adiabatic L) 0.4 O L) 0.2-

"

I.-,

>= 0.60.4o 0.2o

0.0-

~ I

AI

I

1.0--

I

I

I

560 580 600 620 640 T gas inlet (K)

E' a'/R=13900K [ ~ Isothermal

0.0

560

'

'

I

'

I

600 640 680 T gas inlet (K)

Figure 3: Light-off curves when the reaction is the rate determining step -(no heat and mass transfer limitation). Left: adiabatic reactor, no axial heat conduction; right: isothermal reactor (gas and solid at the temperature of'the inlet gas).

59 We observe first that the LO curve.of the adiabatic case is closer to typical experimental results than the curve of the isotl)ennal case. This suggests that even in laborato.ry fixed beds, adiabatic condition can prevail. Second, we observe that E'a is a biased measure of the apparent activation energy in the adiabatic case, whereas it is not (condition (3) ftilfilled) in the isothennal-izase. The adiabatic plug flow behavior can be avoided using a recycle loop reactor at the same GHSV. Since the GHSVper pass is mucli higher, the heat and mass transfer resistances can be low. A recycle rate higher tlian 10 is recommended. Thennocouples located at both faces of the bed cml indicate wlaether the gas phase is mothennal or not. If not, the recycle rate must be increased. Finally, the recycle loop reactor behaves as a continuous stirred tank reactor where the reaction rate is proportional to the conversion at steady, state. Thus, it is the best reactor for kinetic investigations under steady state conditions. Finally, remark that. a recycle loop reactor needs not to operate at the inlet temperature. ~Since the temperature and the compositmn inside the reactor are homogeneous, the LQ curve versus the outlet temperature is meaningful. It remains to l~aow how the type of flow affects the LO curve.

2.6. Effect of backmixing Figure 4 compares the LO curves assuming either plug flow or complete mixing in an^ adiabatic reactor. Under complete mixing condition, the temperatures ot the solid and gas phases and tl~e composition ot the gas are uniform throughout the reactor. Complete mixing prevails ill a recycle loop reactor with a high recycle rate. Generally_liglit-off takes place at a lower temperature when complete mixing prevails. This is because the heat generated by the reaction warms the catalyst everywhere. Conversely, in a p-lug flow reactor, the catalyst located close to the inlet is not wanned enough by the reaction and igalitlon, if any, occurs downstream. Complete ignition, 1.e., lightoff, thus occurs at a higher inlet telnperature. Light-off represents a transition from a low conversion state to a high conversion state due to temperature. When complete mixing prevails, light-off occurs suddenly at a given feed temperature. The LO curve is tlius discontinuous. In plug flow, a liglit-off front appears at the outlet and moves continuously upstream when the feed temperature increases. The LO curve is thus continuous, and smoother than in mixed flow. Except the recycle loop reactor, real reactors, either packed beds or monoliths, are neither plug flow nor mixed flow reactors. However, in small laboratory reactors, heat conduction through the solid phase probably makes the temperature to be uniform as in mixed flow. Conversely, the concentration profiles are those of plug flow. Real LO curves are thus intermediate between those of plug and mixed flow.

60

1.0--

1.0--

.o 0.8o06O

9

o 0.8-

.,..,

l.-,

~

mixing - !

0

9

0.2 0.0 - - ' - " ~ I I 540 560 580 600 T gas inlet (K)

-

0.4-

O

0.4-

6

\

Complet N O9 t.r a n. s f e r lmixing [.. o ~ limitation I

0.20.0-

I

I

540

620

I

I

I

560 580 600 T gas inlet (K)

I

620

Figure 4: Light-off curves f o r a plug flow r e a c t o r and a recycle loop reactor. Left: reaction and transJer are competing. Right: no heat and mass transfer limitations. Figure 5 illustrates the apparent activation energies extracted from the leading part ot the LO curve obtained in an adiabatic recycle 1oo19 reactor when h.eat mad mass transfer limitations take place or not. Wl~en the L O c u r v e is plotted versus the feed temperature, E ' a is biased. Conversely, when the outlet temperature is used, E'a is satisfactory. Remark that about T = 5 50 K mad at low conversion, the inhibiting tenn in equation (1) is much larger than unity. Consequently, E'a must be close to its upper bound. 0

O

~ 9 0.08

~ 9 0.08 >

>

-,

o 0.04 0 r~ 0.00

I

I

I

I

I

o 0.04 0 o 0.00

O 9

0.08

o

O

§ 9

i E, a/R = 19200 K

I

i

I

I

i

0.08 0.04

o ~176 0.00

i

530 540 550 560 570 T gas outlet (K)

530 540 550 560 570 T gas inlet (K)

9 I

I

I

I

530 540 550 560 570 T gas inlet (K)

0.00

I

I

I

I

I

530 540 550 560 570 T gas outlet (K)

Figure 5: Best fit of the leading part of the LO curve in a recycle loop reactor. Upper curves: with transfer limitations. s curves: no transfer limitations. Consequently, in.a recycle loop reactor, the leading part of the LO curve plotted versus the outlet temperature gives a m e a n i n g t u l apparent activation energy. Mass and heat transterlimitations do not induce bias.

61 2.7. The zero-order model

Fiknare 6 illustrates the effect of the reaction order on the LO curve. The zero-order rate expression, r = k (T), used in the figure is derived from (1)_and (2) assuming tlmt tl]e mole fractions of CO and 02 are tlmse.at the inlet ot the catalyst bed and tlmt the adsorption constant is calculated at the inlet gas temperature TO: k(T)xco,0xo2,0 ld ( T ) : P/' + K(To)xco, o,i~ =2

(Ea) ld 0 expk,- RT j

k0xco,0 xo2,o k'0:

k'0 = 1.16 1011 mole.m-3.s-1 at 553 K

(1+ K(To)xco, o i (4)

Ea/R = 12600 K

(5)

where xi 0 is the inlet mole fraction, and k'0 the zero-order frequency factor. At a g!ven teqnperature and low conversion, this makes the zero-order and the LH kinetic rates to be identical. = 1.0O

0.6 ~ 0 ro . 4 9 0.2 0.0

=,0 ~9o 0.8 ,-, > 0.6 o 0.4 9 0.2 ~o 0.0

+ LH k i n e t i c s l ~ 0-order I'~.+

~9 0.8

I

60

'

I

'

I

580 600 T gas inlet (K)

'

4- LH kinetics 1 - 0-order

; ....

,,| .....

, ,,. ...........

~

I

.... I

540 560 T gas inlet (K)

| I

580

Figure 6: Comparison between the light-off curves assuming either a zero-order or the Langmuir-I-[ihshelwood kinetic expression. Adiabatic case, no mass and heat transfer limitation. Left: plugflow. Right: complete mixing. The curves of Figure 6 are very close to each other. This means that lightoff is poorly sensitive to the concentration dependence of the kinetic expresslgn for a given inlet composition. The shape of the LO curve is essentially due to the feedback effect of temperature on conversion through Arrhenius law. Since the LO curve is poorly sensitive to the concentration dependence of the rate law, it can be fitted using, a zero-order rate expression. Figure 7 shows tlae agreement between the sample LO curve and the calculated LO curve in plug flow and mixed flow. The adjusted E'a is close to Ea, and the zero-order frequency factor is close to that given by (5). The model curve for adiabatic plug flow is given by the solution, XCO, of (see appendix): CO d___X= ~ k' (T)H(1 - X) t0 dz z = 0, X = 0

T - TO + ATadX

z = 1, X - XCO

k' (T)

=

k'

( E'a'~ 0expk,-RTJ

(6)

H(1-X) = 1 when X < 1 and H(X-1) = 0 when X = 1. Co and to are respectively the inlet concentration and the residence time of the fluid at a retere.nce temperature,, and ATad is the adiabatic temperature^rise. Wlaen complete mixing prevails, the model curve is given by the solution or

62 (20 k' to Xco = ~ (T);

k'

(T) =

k'

( E'a'~ " 0 expk,-RT ) , T = T O + XcoATad

(7)

XCO = 1 when the solution of (7) is greater than unity. Equation (6) .and (7) are easily solved on any microcomputer, and k'0 mad E'a can be determined using any titting method from standard libraries. Consequently, when there are no mass mad heat transfer limitations, alightoff curve can be interpreted assuming a zero-order reaction rate. Then, correlating the apparent zero-order kinetic constan, t to the inlet composition should give insighf in tile true kinetic expression. :Since the exhaust gas coming ti'om an engine has a composition that lies in a relatively narrow range, tlae zeroorder approximation explains why empirical an.d ear!y published rate expressions lead to good modelling results provided that the activation energies and frequency factors are suitably adapted. 1.0-

......... ;~ + Samplelight-off curve ":::::':~ ~ Fit by 0-order rate k' = 2.21 1011 mole.m-3.s-1 o 0.6E ,~ a/R = 12720 K O OrJ 0.4 ~ 0.2-

= 0.8 O "~

__

0.0 . . . . . . . . .I . . . . . . . I I I 530 540 550 560 T gas inlet (K) "'iv

1.0

~'-

~0.80.6-

9

I

570

+ Samplelight-off curve ] Fit by 0-order rate C , ~ k'0= 1s lO ll mole.m3.sl[t -

Figure 7: Best f.tt of the sample light-off curve by the zeroorder model. Upper curves: complete mixing. Lower curves: plug ~ow. No mass a n d heat transfer limitations, adiabatic case.

0.4O 0.20.0--

60

I

570

I

I

I

I

580 590 600 610 T gas inlet (K) One may thus wonder why further kinetic data are necessary since a zeroorder rate expression fits well tlie LO curves. Let us remark first that, since heat and mass transfer limitations take place in the monolith, the temperatures and compositions are different in lhe wash-coat layer and in the bulk gas. Under mass transfer control, the concentration in the wash-coat layer is smaller than in the gas. Consequently, the zero-order rate constant based on the gas composition becomes lneaningless. Second, the crucial problems are met after light-off when conversion and temperature are high. At high temperature one may argue .that the monolith works under transter',control and tlmt reaction kinetics become secondary. However, Leclerc and Schweich (1993) showed that the reaction

63 becomes the rate determining step at high conversion in a stoichiometric mixture. Finally, oxygen storage in and release from ceria affect conversion in the transient state. Thus, there is probably a need .for kinetic data at high temperattge and conversion, and certainly a need for kinetic data ln~IL'rtransieaLstate. In the next subsections we deal briefly with the required data and the a " ed interpretation problems.

2.8. The quasi steady-state assumption LH rate expressions often rely on the quasi steady state assumption that stipulates that oneelementary step is rate determining whereas the other steps are at equilibri.tm3. The assumption is debatable in the wide temperature range encoun.tered in the monolith, because the rate determining step. may be different according to the temperature level. It would thus be usef[il to know whether the rate expressions obtained at moderate temperature are still reliable at the high temperature and low reactant concentrations observed after light-off l~s occurred. However, care must be taken of the possible transfer limitations, a n d o f the possible catalytically induced homogeneous reactions.

2.9. Characteristic reaction time constants A reaction time constant, either of an overall reaction or of an elementary step is defined by: co tR0 =

r0

where Co .(mol.m-3 of fluid) is a reference, concentrati0n (for example the in!et concentration of CO at To), and r0 (mol.ln-J of fluid.s -l) the reaction rate at the reterence composition and temperature. Remark that fiie rate of reaction of. a heterogeneous reaction must be referred .to the volume of fluid and not to the volume (or mass) of catalyst. Let tR0i be the time constant ot the ith step of. a LH reaction mechanism. If one time constant is much larger than the other, then it defines the rate determining step and the other steps/' are at equilibrium. Without mass and heat transfer limitations, the conversion, X, decreases with the ratio t0/tR0. In an isothermal plug flow reactor X decreases linearly for a zero-order reaction, exponentially for a first-order reaction, etc. (See standard textbooks on chemical kinetics and chemical reaction engineering), Thus, the analysis of X versus to (i.e., GHSV) allows estimating tR0. Wlaen the reaction order is not known, a very rough approximate ot tR0 is given by to when X = 0.5. In other words, the GHSV and the TLO yield an estimate of an overall reaction time. For example, Figure 2 gives a light-off temperature about 590 K that yields tO = 7.3 ms .(from GHSV = 75000 h - r) which is in agreement with tR0 - 5.3 ins (from equations (1) and (2)). For obtaining the time constants o f elementary steps, Temporal Analysis of Products (See Ansell et al., 1994) is probably the best method. Oxygen Storage C.apacity measurements can give the amount of oxygen available in the cataIyst but nothing is known concerning the rate at whicli tlais qxygen is available. Rhodiuln is lolown to be more or less oxidized according to the composition ot the gas phase, and the oxidation state of rhodium affects the reduction rate of NO. Consequently, it would be usefid to know the time

64 constants of oxygen storage in and release oxidation/reduction reaction ofrhodium.

from ceria,

m~d of the

If the above time constants are much smaller than the time constants of the main reactions, then the rates of the latter can. be assmned to depend on the current composition ot[ the gas pl.mse. If not,, t!ae instantaneous activity of t!le catalyst depends on its history, and the rates ot the main reactions depend on the fluid composition and on some composition variable of the solid phase (available stored oxygen, oxidation state of rhodium for example). Few papers are devoted to the previously mentioned transient surface processes. Herz (19.87) proposed the first simple and efficient model.for oxygen storage in ceria and trm~sient deactivation ot-the noble metal. /Xmother oxy.gen storage model was recently proposed by Pattas et al. (1994). It seems that there is not-hing about oxidation and reduction of rhodium. W e will just outline what could be Llone for NO reduction over partially oxidized rhodium following Herz's approach. Let qOxbe the fraction of oxidized rhodium, and rRed be the rate of NO reduction on fidly reduced rhodium. We assume that rRed depends only on the gas phase composition. The rate of NO reduction on partially reduced rhodium can be: r = (1-qOx)rR~d (8) Let tRed be the reduction time of rhodium. Assuming a first-order rate for rhodium reduction, we have: d0ox _ 0Ox -Koxf(Po2) tRed (9) dt where KOx is a pseudo-equilibrium constant of rhodium oxidation by 02. This does not mean that Rh - Rh203 forms a solid mixed phase, but ratlier that the amount of reduced rhodium can depend on oxy.gen partial pressure, at least in a certain range defined by function f(Po2). Eqtmtiojls (8) and (9) define the rate of NO reduction under unsteady conditions. :Steady state experiments at various oxygen concentrations and temperatures would give KOx(T). Temporal Analysis of Products (TAP) experiments at various temperatures would probably give tRed(T ). TAP experiments at various oxygen concentrations would also tell wlletller the first-order law (9) is valid or not. The same approach could be used to model the effect of SO2. According to the time dependence of PO2, the quasi steady state assumption holds or not. When PO2 is constant and qOx = Koxf(Po2), .(9) is i.dentically fidfilled. When PO2 varies periodically with a period, P, much larger than tRed, the solution to (9) is again close to q0x = Koz~f(Po2). In these two cases, r depends only on the gas phase composmon and tlae quasi steady s.tate assumption holds. Conversely., if P is smaller than or of the or~ter of tRed, then qOx is no longerproportional to PO2 because of .(9), and r becomes nnplicitly time-dependent. This example shows that a transient surface process becomes important when its characteristic time is greater or equal to the clmracteristic time ot some external phenomenon. Since composition or temperature variations with a frequency higher than 1 .Hz are considerably damped b.y hydrodynamic and transfer processes, and by the engine itself, it is expected that quasi steady state can be assumed for surface processes which have characteristic times smaller than one second.

65 Simple transient state experiments in laboratory plug flow reactors can .qualitatively tell whether the surface processes mentioned above are lnstantmleous ornot. For example, a step composition change can lead to tw.o types of results. Either the outlet composition fdllows what is expected from the stead.y state rate equations or not. In the former case, one may assume quasi steady state. In the latter case, one is facing a slow su.rface step (oxidation/reduction of rhodium, oxygen storage/release, transient deactivation By SO2, etc.) that attects the main reaction meclmnism. Intrinsically_ fast reactions can serve as probes to measure the reaction time of a transient surface process. According to equations (1) and (2), CO oxidation has a characteristic time smaller than 0.1 s above 520 K. Switcliing from a lean CO/O2 feed to a rich feed, and then studying the conversion of CO versus time gives the amount and the characteristic time of the oxygen released from the catalyst (See Herz (1987)., Smedler et al. (1993)). In such an experiment care must be taken first with the water gas shift reaction when water is in the feed, and second with the possible heat and mass transfer limitations. Measuringreaction time constants is a raw approach to the mechanism and rate expression. However, since tR0 is proportional to the reciprocal of the rate, it must obey Arrhenius law. This enables one to measure the reaction time at moderate temperature and then to extrapolate the result to a realistic temperature range to know whether the surface process is at equilibrium or not. Experiments made with an oscillating feed composition mimic what can happen in a real converter. However, their mechanistic interpretation is otten difficult. It is sometimes argued tlmt it the result of such an experime!a.t is different from the result of an experiment performed at the average composmon, then there is some "storage" phenomenon that is overlooked at steady state. Let us show tlmt this conclusion can be wrong witla the example of CO oxidation in a plug flow reactor. Consider a square wave feed made o f 4% CO, 0% 02 in the firts half period and 0% CO, 2% 02 in the second. The average feed is 2% CO, 1% 02 that leads to the LO curves shown above. In the oscillating regime, when the adsorption and desorption steps are instantaneous CO is never m contact with 02 and tile conversion is zero whatever the temperature. This clearly means that the oscillating feed and the average feed do not give the same result when the quasi steady state assumption holds. Conversely, if and only if there is. an adsorption or desorption time constant tlmt is larger titan the cycle period, then CO conversion is nonzero. In the latter case we may speak of an 02 or CO storage effect either on the metal or in ceria. A reaction time estimate is reliable only when the feed system, the reactor, and the detectors have an overall time constant smaller than the reaction time under study. If not, no conclusion can be drawn. This is illustrated by the oscillating feed experiment performed in a recycle loop reactor when the period is smaller titan tlie residence time of the fluid. In the latter case, the two alterl)ating feeds are mixed and CO conversion is nonzero even under quasi steady state conditions. The same problem arises when the feed si~aal is not a pertect square wave owing to mixing in the inlet tubes. A plug flow instead of a recycle loop reactor is then recommended, and any dead volume or by-pass.must be eliminated from the flow system. Furthermore, it must be kept in mind tlmt CO or NO detectors can have intrinsic time constants of a few seconds that often mask smaller reaction times. Finally, the heat storage time constmat can be large

66 il~ responsible for the delayed light-off at start-up of the engine!). Conversely, allows the observation ot reaction times shorter than one second in an isothennal catalytic bed. 2.10. Further remarks

Reversible poisoning by 8 0 2 is a typical ~ansient storage/release phenomenon that depends on the oxidizing ab-ility ot the fluid. Here again, determining poisoning time constants versus temperature and SO2 and-02 contents oftlie feed would be helpful. If the zero-order method of section 2.6 reveals to be efficient, then it should be used to compare fast and slow 9xidizing hydrocarbons (alkenes and methane for example). It is expected tlmt the .activation energy is COl\stant in a homologous series of hydrocNbons. Then, tl~e ratio ot the rates of reaction should 15e close to the ratio ot the zero-order kinetic constants determined with the LO cmves. This fortunate situation would enable one to scale the rates of oxidation of various hydrocarbons with respect to a standard hydrocarbon (propylene for example). Finally, let us recall that kinetic investigations with a complex mixture that involves multiple reactions are an overwhehning task..It is better to work with simple mixtures for obtaining reliable rate expresslgns. Then, mechanistic considerations should indicate how the rate expressions generalize for the omplex mixture. However, the .simple mixture must at least contain water that is own to interact witll the catalyst. This means tlmt the water gas shift and the steam reforming reactions are unavoidable. IOmwing the kinetic importance of the latter reactions remains a challenge. 3. EXTERNAL MASS AND HEAT TRANSFER DATA IN THE MONOLITH

Heat and mass transfer processes have been extensively dealt with in many papers (See a brief review ill Schweich and Leclerc, 1993). In most models, heat an~t mass transfer processes are accounted for by coefficients that are given by non-dimensional numbers: Sh -

kDDh Dm

Nu -

hDh X

(10)

Sh and Nu are the Sherwood and Nusselt numbers, kD and h the mass and heat transfer coefficients, Dh the hydraulic diameter of a chamM, Dm and 1 the molecular diffusivity and the heat conductivity of the fluid. Models for simultaneous lmninar flow and transverse diffusion yield for a long monolith: NuAShA3 (11) However, based on experimental results, Votruba et al. _(1975) pointed out that Nu and Sl~ are probably smaller than 3. More recently, Ullah et al. (1992) and Belmett et al. (1992) gave other experimental evidence based on CO and C3H8 oxidation respeetivel;r For a monolith 15 cm long operatecl at Re = 250 (close to the upper limit), Ullah and Belmett correlations give S1)A 1 and Nu A 0.2 respeetiveIy. These low values were obtained by ~ting the experimental results with a first-order rate expression. Under reaction control, the apparent

67 rate constant is the reaction rate constant, whereas under mass transfer control it gives the Sherwood lmmber..The dependence of the apparent rate constant on temperature yields the rate determining step. At low temperature, chemical regime preyalls and the rate. constant obeys A2rrhenius law. At high temperature, mass transter controls and tlae apparent activation energy is close to zero. Ullali et al. reported that they worked in a temperature range where the apparent activation energy was c!ose to zero wit-h no further quantitative details. Conversely, Belmett et al. reported an apparent activation enerav about 36 kJ.mole -1 in the mass transfer regime instead of 90 kJ.mole -1 in "file chemical regime. The latter authors finally attributed the low Sherwood numbers to the possible/presence of homogeneous reactions. Figure 8 illustrates another possible explanation using CO oxidation in an adiabatic p-lug flow reactor.

2

~

[]

Cl

0-1-

~~

- 2OOOK I[E,a _ '4O0O K I -

m

[] I

1.30

O

C1

9 In(k)

-

I

'

2.0

[]

[] [] []

Sh

'

ill

3.0

-

I

1.40 1.50 1/T (K)

'

I

C

1.60xlO 3

0"2

1.0

0.0

Figure 8: Arrhenius plot of the apparent first-order rate constant (full dots) and interpretation of the rate constant as a Sherwood umber (open dots). mperature range ( 3 4 0 520~ above light-off temperature.

The catalyst is ignited on the fifll range of temperature. At low temperature (340~ the rate constant obeys Arrhenlus law with a consistent apparent activation energy. The corresponding Sherwood number is very low and it does not make sense. At high temperature (520 C), E'a is still nonzero .and the corresponding Sherwood-number is still sm.all~r than 3. This shows that obtaining fifll mass transfer control is difficult, and tlmt unusually low Sherwood numbers can be due to a partial kinetic control. 4. INTERNAL MASS TRANSFER RESISTANCE This problem was dealt with by Schweich and Leclerc (1991) and Leclerc and Schwelch (1993). Most models assume that there is no internal diffilsion liLnitation because the wash-coat layer is "thin". Presently, it is not known wl~etlaer this assumption holds, and decisive experiments with different washcoat thicknesses at a given metal loading should be undertaken. The experiments should be carefully performed to avoid confi~singintemal and external mass transfer resistances. A dedicated reactor should probably be desig0ed. It could be a continuous stirred tank reactor (mechanical stirring) containing a slaeet of wash-coated substrate. If the rate of reaction depends on tlie wash-coat thickness, and not on stirring speed, then internal diffi~sion resistance prevails.

68 5. HYDRODYNAMIC CONDITIONS

The consequences of the flow pattern on the experimental results are strikingly illustrated by Figure 4. It is thus of prime importance to control the tlow pattern or at least to be aware of the possibIe hydrodynamic problems. Experiments with laboratory monoliths of small cross-section area can lead to biasedresults due to an uneven flow distribution in the chmmels, especially close to the reactor wall. The wash-coat of the outer broken chalmels should be scraped away, and the void between the reactor wall and the monolith should be caregully plugged. To minimize wall effects, the diameter of the monolith should be ten times flie.chamlel diameter at least. Plug flow must prevail in a packed bed of crushed catalyst. The bed length and radius should be more than 50 and 10 particle diameters respectively, the flow resistance of the bed. support must be unitonn throughout its cross-section, and tl~e particle size distribution must be as narrow as possible. Otherwise, there can be-by-passes or dead. volumes. These hydrodynalnic problems are overcome in a recycle loop reactor because the same physical and cliemical conditions prevail everywhere. In commercial converters, the fluid distribution Call be strongly nonuniform owing to the short inlet cone between the exhaust pipe and the monolith (Howitt and S-ekella, 1974; Wendland and Matthes, 1986),Uiffortunately, few are known concerning the dependence of the fib w maldistribution on monolith properties, working temperature, and flowrate. Li et al. (1991) provided some flow field characteristics using PHOENICS software. Bella et al. (1991) included the oxidation reactions in the description ot the flow field. These papers describe case-by-case silntAlations, and no correlations between the operating cond!tions and the fluid distribution are given, l~urtl~er experimental and simulation works on this subject would be welcome. 6. CONCLUSIONS

Kinetic expressions are probably the most crucial data for model reliability. These data are certainly different trom one catalyst to the otller. However, the reactions are the same, and the catalyst formulations are similar. This suggests that the structures of the rate expressions are probably independent o f the catalyst, whereas the parameters are depen.dent. Elucidating the structure of the rate expressions at steady state, estimating tl~e time constants ot transient surtace processes and reversible poisoning~ knowing whether internal diffilsion is a limiting process would be more sign.lficant cgntributions than accumulating lightoff curves obtained with complex mixtures. Although tllese curves are teclfilically meaningful, they calmot be interpreted from a scientitlc point of view, especially when tlie reactor behavior is not well controlled. This is ilelnonstrated by-Figures 1 to 7 which show that the light-off temperature is somewhere between 560 and 630 K depending on the reactor behavior (hydrodynamics and transfers). The second challenge concerns hydrodynamic data in commercial converters. The "flow distrilSution index" o f Wendland and Matthes (1986) and Bella et al. (1991) is a first ap.proach to the problem. However, filrther work is necessary to correlate this index to the operating conditions. As long as flow maldistrlbution is not accounted for in the models, simulation of vehicle tests will not be reliable.

69 LIST OF SYMBOLS

Co Dh Dm ~G~t

inlet concentration hydraulic diameter of a channel molecular diffilsivity apparent activation energy titted activation energy, SV gas hourly space velocity H(X) Heaviside step function laeat transfer coefficient K adsorption constant Ko p re exponential factor of the adsorption constant KOx rhodium oxidation equilibriuln constant k kinetic rate constant k' apparent kinetic constant ko frequency factor k'o apparent frequency factor kD mass transfer coefficient L monolith or bed length Nu Nusselt number PO2 oxygen partial pressure R ideal gas constant Re Reynolds number r rate of reaction ~ e d NO reduction rate on fully reduced rhodium Sherwood number T temperature TLO light-off temperature TO inlet temperature Tw wash-coat temperature t time to residence time of the fluid tR0 reaction time at inlet conditions tRed reduction time of rhodium UB, uMfluid velocity in the packed bed, in the monolith w wash-coat tl-fickness X conversion Xw conversion in the wash-coat layer mole fraction of species j xi,0 mole fraction at inlet z reduced distance z' distance Greek symbols DHads adsorption enthalpy DTad adiabatic temperature rise eM 9pen frontal surface area of the monolith eB mtergranular void fraction in the packed bed volume of catalystper unit volume of intergranular gas ~Ox traction of oxidlzedrhodium gas heat conductivity

70 LITERATURE CITED

Ansell G.P., S.E. Golunski, J.WX. Hayes, an.d A.P. Walker: The mechmlism of the lean NOx reaction over Pt-based catalysts. CAPoC 3 Symposium, April 1994, Brussels, Belgium. Bella G., V. Rocco, M. Maggiore, F. Stella, and F. Succi: Automotive catalytic converter performance evaluation: a computational approach. ATA lnge~neria Automotoristica 44, 242 1991. Bennett ~.J., R.E. Hayes, ~;.T. Ko]aczkowski, and W.J. Thomas: An experimental and tlieoretical study of a catalytic monolith to control automobile exhaust emissions Proc. R. Soc. Lond. A, 439 465, 1992. Froment G.F., and K.B. Bischoff: ~helnical reactor analysis and] design, J. Wiley, New York, second Ed. Heck R.H., J. Wei, and J.R. Katzer: mathematical modelling of monolithic catalvsts AICI~ J., 22, 3,477, 1976. Hegedus i~.: ]'emperature excursions in catalytic monoliths, AIChE J., 21,849853. Herz R.K.: Dynamic behavior of automotive three-way emission control systems. In "Catalysis and Autolnotive Polution control", A. Cmcq and A. Fremlet Ed., Else,;,ier, 1987, pp. 427-444. . . Howitt J.S., and T.C. Se]~ella: Flow effects in lnonolithic honeycomb catalytic converters, SAE paper 740244, Automotive Engineering Congress, Detroit, 1974. Leclerc J.P., and D. Schweich: Modelling catalNic monoliths for automobile ~cl~l?~tfw~ ,s~fe Netherlands, p. 547-576, i993. "_ " Li P., G. Chui, and J.D. Pakko: A numerical study of automotive catalytic converter internal flow. In "4th International PHOENICS User Conference", CHAM Ed., P 189-230, 1991. Mabilon G., D. Durand, and Ph. Courty: Inhibition and poisoning of postcombustion catalysts by. alkynes: a clue for understanding their behavior under real exhaust conditions. CAPoC 3 Symposium, April 1994, Brussels, Belgium. Pattas K2.N., A.M. Stalnatelos, P.K., Pistikopoulos, P.C. Koitsakis, and P.A. Konstandinidis: Transient modeling of 3-way catalytic converters. SAE Paper 940934, 1994. Schweich D., and Leclerc J.P.:,, Flow,. heat and mass. transfer in a monolithic" " catalytic converter. In Catalysis and Autolnotlve Pollution Control II", A. Crucfl Ed., Studies in surface science and catalysis, Elsevier, p. 437, 1991. Smedler G., S. Eriksson, M. Lindbald, H. Bemier, S. Lundgren, and E. Jobson: Deterioration.of three-way automotive catalysts, Part "II- Oxygen storage capacity at exhaust conditions. S1E Paper 930944, 1993. Subramanian B., and A. Varlna: Reaction kinetics on a colnlnercial three-way catalyst: the CO-NO-02-H20 system, Ind. Eng. Chem. Proc Des. Devel., 24 512 1985. Ullah l~., s.ib. Waldram, C.J. Belmett, and T. Truex: Monolithic reactors: mass transfer measurements under reacting conditions. Chem. Eng. Sci., 47, 9, 1992. .. Voltz S.E., C.R. Morgan, D. Liederlnan, and S.M. Jacob: Kinetic study of carbon monoxide and propylene oxidation on platinum catalysts, Ind. Eng. Chem. Proc. Res. Dev., 12, 295, 1973. Votruba J., O. Mikus, K. Nguen, V. Hlavacek, and J. Skrivanek: Heat and mass transfer in honeycomb catalyst - II. Chem. Eng. Sci., 30, 201, 1975.

reeaicStSor~176

al ~eaas~~

71 Wendland D.W., and W.R. Matthes: Visualization of automotive converter internal flow. SAE paper 861554, International Fuels and Lubricants Meeting and Exposition,-Philadelphia, 1986. APPENDIX

Using the film model and assuming plug flow, the mass balance equations for a reactant are (See Heck et al., 1976, Froment and Bischoff, 1990 for example): dX C0UB dz' = r(Xw' Yw)4) in a packed bed (A1) dX 4 COUM"d'~" = r(Xw' Tw ) D--'-h

in a monolith (A2) where C0uM or C0uB is the specific lnolar feed flowrate of reactant, C0 the inlet concentration of reactant, uM/B the interstitial velocity, X the reactant conversion in the gas phase, Xw and Tw the conversion ana the temperature in the wash-coat layer. When there are no mass and heat transfer resistances, Xw = X, and Tw = T. Since C0uM/B is independent of the temperature, CO and uM/B can be calculated at any reference temperature. The GHSV obeys: GHSV ~

eMUNI _ 8BU~3

L

L (A3) where eM/B is the void fraction in the monolith or catalyst bed. The proportionality constant depends on the time units. A fixed bed and a monolith operated at tlie same feed composition, temperature and GHSV will have similar behaviors when equations (A1) and (A2) become identical. This implies: 4W~M =~;B~) Dh

(A4)

The behaviors of the monolith and of thepacked bed are not identical in general .because Xw mid Tw are not still specified. If there are no heat and mass transter limitations, and if the gas temperature is the same in the two reactors, then they behave identically. Let L be the length of the catalytic system and z=z'/L be the reduced distance. (A1) and (A2) become respectively: Co dX_r(Xw,Tw) 4W

t 0M dz

K

Co dX_r(X t 013 dz

Tw)~ w,

(A5, A6)

where t0M/B = L/uM/B is the residence time of the fluid in the t~!mse. Assuming no heat and mass transfer limitations gives Xw = X and Tw ga~?. w lien the reactor is adiabatic, the gas temperature increases proportionally to the conversion (Hegedus, 1975): T - TO+ ZXTadX

(A7)

uations (A6) and .(A7) give .(6) when fiX,T) =.k'(T) H(lzX). In the recycle oop reactor, the derivative dXMz is replaced by the ratio ot the variables, i.e., XCO. This gives (7).


A. Frennet and J.-M. Bastin (Eds.) Catalysis and Automotive Pollution Control I11 Studies in Surface Science and Catalysis, Vol. 96 1995 Elsevier Science B.V.

73

R E A C T I V I T Y OF STEAM IN E X H A U S T GAS CATALYSIS. PART II : SINTERING AND R E G E N E R A T I O N OF Rh AND PtRh CATALYSTS IN P R O P A N E O X I D A T I O N

J. Barbier Jr. and D. Duprez Laboratoire de Catalyse en Chimie Organique URA CNRS 350 40 av. du Recteur Pineau , 86022 POITIERS Cedex FRANCE Tel : (33) 49 45 39 98.

ABSTRACT PtRh catalysts were prepared on different supports composed of A1203, CeO2, ZrO2 and NiA1204. The variations of the activities in propane oxidation and steam reforming were used to obtain some indication concerning the surface state of these catalysts after thermal treatments at high temperature in an oxidizing and in a reducing medium. Cyclopentane hydrogenolysis was also carried out to observe the changes in the rhodium surface state. Platinum was the metal which catalysed the direct oxidation of propane while rhodium was the key-component in steam reforming catalysis. The treatment at 800~ in an oxidizing medium induces a very important decrease of Rh area linked to the fact that rhodium in its oxidized form (Rh 3+) can diffuse into the support. This phenomenon is more marked on A1203 and, to a lesser extent on CeO2-A1203, than on the other supports. On the other hand, oxidative treatments lead to an increase of the particle size of platinum, and temporarily to an enhancement of the oxidation activities. After a treatment in a reducing medium at high temperature (T>700~ the steam reforming activities can be recovered by extraction of rhodium from the support, with two exceptions however : Rh/CeO2-A1203 and PtRh/ZrO2 catalysts. This treatment has pratically no impact on platinum activities in oxidation except for the catalysts supported on NiA1204 which are deactived. Cyclopentane hydrogenolysis confirm all the above results.

1. INTRODUCTION PtRh catalysts are COlmnonly used in catalytic converters for eliminating pollutants (CO, hydrocarbons, NOx) from exhaust gases [1]. In the first part of our w o r k [2], we investigated, on P t ( l w t . - % ) , Rh(0.2wt.-%) and

74 Pt(lwt%)Rh(0.2wt%) catalysts supported on A1203 and CeO2-A1203, carbon monoxide and propane oxidation by oxygen (direct oxidation), by steam (water gas shift and steam reforming) and by a mixture of oxygen and steam (oxy-WGS and oxy-steam reforming). Steam can be considered a cor-eactant of oxidation during rich-phases (lean in O2) [3-5]. In oxy-steam conversion of propane, we showed (fig. 1) that propane oxidation was catalyzed by platinum (between 200 and 350~ while rhodium was the key-component in the catalysis of steam reforming (between 350 and 600~ Ceria was an excellent promotor of steam reactions [3, 6], particularly when this reaction was carried out in the presence of oxygen. Therefore, the steam reforming activity is an excellent indicator of the rhodium surface state since the activity systematically decreases when the metallic rhodium area decreases [7]. On the other hand, oxidation activity is a more complex indicator of platinum surface state because there exists an optimum dispersion [8, 9]. Metal sintering constitutes a very significant cause of loss in catalyst activity owing to the reduction in the metallic area [10,11 ]. The aim of this work is to study the sintering of Rh and PtRh catalysts by means of oxidation and steam reforming activities in propane conversion. Changes in the steam reforming activity have been compared with those obtained in cyclopentane hydrogenolysis, a reaction extremely sensitive to the state of Rh in the catalyst [12]. C3H8 conv. (%) 100 -

El E

80 Direct oxidation 60 40

9 1 4 9I

20

00

[] El

[]

[]

.

Steam reforming

[]

,..--.~...~_~ .m 0

~!,

200

[] [] I

I

300 400 Temperature (~

I

500

600

Fig 1 9Oxy-steam reforming o f propane on PtRh/CeO2-AI203

75 2. E X P E R I M E N T A L

2.1 Catalysts Five different supports were used : (i) a gamma-alumina (120m2 g-l) which was impregnated with an aqueous solution of cerium nitrate to obtain (ii) a 12wt.-%CeO2-A1203 after calcination (100m2 g-l); (iii) a zirconia (40m2 g-l) supplied by Degussa, (iv) a support prepared by coimpregnation of a Ni(NO3)2 and an Al(NO3)3 aqueous solution on an alumina (200m2 g-l) so as to obtain after calcination (1000~ air, 24h) a 8.5wt.-%NiA1204-A1203 support and this support is impregnated with an aqueous solution of cerium nitrate to obtain (v) a 12wt.-%CeO2-8.5wt.-%NiA1204-A1203 support after calcination. These supports (A1203, CeO2-A1203, ZrO2, NiA1204-A1203 and CeO2-NiA1204-AI203) were crushed and sieved to 0.1-0.2 mm. They were used to prepare two series of catalysts by impregnation or coimpregnation with aqueous solutions of rhodium chloride and chloroplatinic acid. The catalysts were dried at 120~ then calcined at 500~ under an air flow and prereduced in H2 at 450~ The metal loadings were Rh(0.2wt.-%) and Pt(lwt.-%)Rh(0.2wt.-%). A Pt(lwt.-%) on gamma-altmaina (120m 2 g-l, 0.10.2mm) supplied by I.F.P. (French Institute of Petroleum) was also used for certain experiments. Table 1: Catalyst co m positions Pt Symbolic (wt.-%) Name 1 Pt/A Rh/A 0 0 Rh/CeA 1 PtRh/A 1 PtRh/CeA 1 PtRh/Z 1 PtRh/ANi PtRh/CeANi 1

Rh

Support

0 0.2 0.2 0.2 0.2 0.2 0.2 0.2

A1203 A1203 A1203 +CeO2 (12wt.-%) A1203 A1203 +CeO2(12wt.-%) ZrO2 A1203+A1204Ni(8.5%) A1203+A1204Ni(8.5%)+CEO2(12%)

(wt.-%)

76 2.2 Catalytic reaction

Before each run the catalyst samples were heated in air for l h at 450~ Propane oxidation was carried out in a flow reactor under the following conditions : (i) catalyst bed : 40mg diluted in 360 mg of eordierite (0.1-0.2 mm). (ii) Feed gas (in vol-%) : C3H8, 0.4 ; O2, 0.8; N2, 98.8. (iii) Gas flow-rate : 380em 3 min-1 (volume space velocity : 250,000h-1). Temperature-programmed reactions were carried out from 150 to 900~ using a 4~ min-1 temperature ramp (1 atm.). Analyses were carried out by gas chromatography : CO2, CH4 and C3H8 on Porapak Q (0.7m, 1/4 in.; 25~ or 100~ cartier gas HE), CO, O2, N2 and CH4 on molecular sieve 5A (0.4m, 1/4 in.; 25~ carrier gas H2), H2 on molecular sieve 5A (lm, 1/4 in.; 25~ carrier gas N2). C3H8 conversions were determined from the mass balance of carbon-containing products and verified by the disappearance of the C3H8 peaks in the ehromatograms. The main reactions considered here were direct oxidation (1), C3H8 steam reforming (2) and W.G.S. (3). C3H8 + 502 . . . . . > 3CO2 + 4H20 (1) C3H8 + 3H20 . . . . . > 3CO + 7H2 (2) CO + H20 . . . . . > CO2 + H2 (3) Reactions (2) and (3) occurred via the water produced in reaction (1) : even in the absence of steam in the inlet gases, typical light-off curves like those in Fig. 1 were obtained. Specific activities and activation energies in oxidation and steam reforming were determined at low conversion. Specific activities were calculated at 200~ for direct oxidation and at 300~ for steam reforming. 2.3 Sintering and regenerating conditions

The oxy-steam reforming reaction was carried out on : - flesh catalysts (450~ 02 (3vol.-%); lh)) (FRESH) - oxidized catalysts (650~ or 800~ 02 (3vol.-%); lh) (OX650 or

ox800), - oxidized (800~

or 900~

O2 (3vol.-%); lh) and then reduced catalysts (700, 800 H2 (3vol.-%); lh)(RED700 or 800 or 900).

77

2.4 Cyclopentane hydrogenolysis This model reaction was carried out "in situ" on flesh or sintered catalysts (OX800 and RED900). The catalysts were prereduced in H2 (lh, 300~ 30cm3 min-1). Cyclopentane hydrogenolysis was performed in a pulse flow reactor under the following conditions : (i) catalyst bed : 40mg diluted in 360mg of cordierite (0.10.2 mm); (ii) cyclopentane injection : 11 lamole per pulse; (iii) hydrogen flow rate: 30cm3min-1; (iv) temperature range 170-330~ Under these conditions, the only reaction product was n-pentane analyzed by gas chromatography on a reoplex 400 column (2m, 1/8 in., 50~ carrier gas H2). The specific activities in cyclopentane hydrogenolysis of catalysts were calculated at 200~ 3. RESULTS AND DISCUSSIONS

3.1 Rh/A catalyst Figure 3 shows the light-off curves of Rh/A after different treatments. On this catalyst, the activities in steam reforming cmmot be determined because the two regions (oxidation mad steam refonning) are not sufficiently discrete : Rh being a poor oxidation catalyst, the two reactions occur pratically at the same temperature. Increasing the severity the treatment in 02 induces a very important deactivation of the catalyst (FRESH, OX650 and OX800 in Fig.2). At low temperatures (T CeO 1 72

/ /

673

c) - - = - - CeO 2 -> C~O 3

e), 473

1.8

I

1.9 x in C e O x

2.0

100

500

900 Temp / K

1300

Fig. 7. Some thermodynamic data for Ce02. Left: Phase diagram for Ce-O. Right: Equilibrium conditions for Ce02 reduction It is noteworthy that this defective phase is formed in all our M/CeO2 samples whatever the metallic phase used (Rh, Pt or even Au) and either if chlorine is present or not, thus suggesting a thermodynamic control of the whole reduction process. Moreover, reduction up to 1200K leads in all our samples, including

120 now also the CeOz support, to a stoichiometry close to CeO~.Ts that, according to the data shown in the same figure, corresponds to a new phase of the same homologous series ( with n=9, V0++= 11%). Some differences are observed of the behaviour of the generated CEO1.82 phase at in the two sets of samples (N, C1). In principle, the "Cl-profiles" in Fig. 6 for all the Cl-samples are very similar and indicate that the C1 is concentrated at the surface while the amotmt of hydrogen incorporated into the ceria (as hydride-like species[19]) is very different in both set of samples. Data in Fig.5 suggest that hydrogen is incorporated to the CeO~.sz, into the V0++ existing throughout the whole structure of the defective phase. The amotmt calculated from this figure (using H/M ca. 2.1) corresponding to the filling of ca. 80% of these vacancies with hydrogen which is only removed at T>573K. However, incorporation of 1-12 does not occur when C1 is present at the ceria support indicating that chlorine at the surface of these samples is able to prevent the access of this hydrogen into the defective CeO~.82 structure. This is probably due to the incorporation of the C1 itself to the V0++ thus stabilizing Ce 3§ species as could be detected by XPS after reoxidation and is also suggested by the sharpening of the Cl(2p) signal. Moreover, the higher reduction observed by XPS in these Cl-samples should be ascribed to this fact, which might prevent Vo+§ diffusion. Let us now ask why "junction effects" do not seem to control the reduction of M/CeO2 mad, probably, methanol synthesis on these catalysts? In our view two points should be considered to answer this question. First, Frost in his model makes the assumption that "vacancies are concentrated at the surface of the thin oxide overlayers" (i.e layers of the 0.5-5 nm thickness). Clearly, this is not the case in our samples. Though V0++ (and Ce 3+) should be initially created at the surface, where according to recent calculations by Catlow et al [11] they are more easily formed (particularly in the less stable 110 planes) they readily diffuse at T > 573K to the bulk (while lattice oxygen (O--)moves toward the surface as could be expected for the well l~aown behaviour of ceria as an ionic conductor ) thus decreasing the surface concentration of V0++probably by one or two order of magnitude. At least for our high surface area ceria, formation of the nonstoichiometric stable Ce,O2,_2 phases seems to act as the driving force again surface segregation of the oxygen vacancies. Second, during hydrogen reduction as well as during the synthesis of methanol when, besides CO/CO~, an excess of hydrogen is in contact with the catalysts, we calmot discard that the generated M-CeO~ "Shottky" junctions were reduced to the same value, detennined by the hydrogen work function at the M CeOz interface and by the electron affinity of the ceria support, thus leading to a similar final reduction state of the ceria for all metals ( as actually observed in our

121

samples). This fact has been observed by Aspnes et al [20] in Rh/TiO2, Pt/TiO2 (and several others) metal-semiconductor pairs and by ourselves in Rh/TiO2, and PtJTiO2 catalysts [21] where EPR shows that a complete change of contact character from rectifying (Schottky) to Ohmic occurs upon exposure to hydrogen at 300K as detected by generation of T? + species that readily disappear when hydrogen is removed from the gas phase. Though hydrogen doping of the TiOz [22] (and CeO2) can not be ruled out as the origin of this ambient gas-induced change, Aspnes et al [20] conclude from electrical measurements that the general mechanism, that bears on all contacts studied, is the change in the surface dipole component of the metal work fimction upon changing the ambient gas. So, we must conclude, in agreement with Lambert et al [7], that "the most natural explanation for the high activity in methanol synthesis of their Cu/CeO2 catalyst, and the lack of activity of Ag/CeO2 and Au/CeO2, is that active sites involving copper species are responsible for the reaction" while the crucial role for ZnO, ThO2, or CeO2 should be to raise the effective partial pressure of hydrogen on the catalysts under reaction conditions as suggested by Bttrch et al. [23]and as we had also previously reported for Rh/TiO2 catalysts [24] where we have shown that hydrogen, incorporated as hydride-like species into V0+§ acts as a "reservoir" for suppling hydrogen in the reaction to produce methanol. 5. ACKNOWLEDGMENT

We thank the CICYT (Project MAT91-1080-CO3-01) and CEE (Project SCI*-CT91- 0704(TSTS)) for financial support

REFERENCES

J.C. Frost, Nature,334 (1988) 557 B. Harrison, A.F. Diwell and C. Hallett, Platinum Metals Rev., 32 (1988) 73 A. Laachir, V. Perrichon, A. Badri, J. Lamotte, E. Catherine, J.C. Lavaley, J. E1 Fallah, L. Hillarie, F. Le Normand, E. Quemere, G.N. Sauvion and O. Touret, JCS Faraday Trans., 87 (1991) 1601. A.Trivarelli, G. Dolcetti, C. Leitenburg, J. Kaspar, P. Dinetti and A. Santoni, JCS Faraday Trans. 88 (1992) 1311. R.M. Nix, T. Rayment, R.M. Lambert, J.R. Jennings and G.Owen, J.Catal.,106 (1987) 216. E.A. Shaw, T. Rayment, A.Walker, R.M. Lambert and J.R. Jennings, J.Catal., 126 (1990) 219.

122

10 11 12 13 14 15 16 17 18 19 20 21 22 23 24

E.A. Shaw, A.P. Walker, T. Rayment and R.M. Lambert, J. Catal., 134 (1992) 747 H.C. Yao and Y.F. Yao, J. Catal. 86 (1984),254. J. Sofia, A. Martinez-Arias, J.C. Conesa, G. Munuera and A.R.Gonzalez-Elipe, Surf. Sci. 251/252 (1991) 990. M.F.L. Johnson and J. Mooi, J. Catal. 103,(1987),502; ibid 140 (1993) 612 T.X.T. Sayle, S.C. Parker, and C.R.A. Catlow, JCS Chem. Comm. (1992) 977. P. Malet, A. Caballero, J. Chem. Soc., Faraday Trans. 1, 84 (1988) 2369. J.M. Rojo, J. Sanz, J. Soria and J.L.G. Fierro, Z. Phys. Chem (NF) 152 (1987) 149. J.P. Holgado, R. Alvarez and G. Munuera (to be published) L. Tournayan, N.R. Marcilio and R. Frety Appl. Catal. 78 (1991) 31. G.Munuera, A.R.Gonzfilez-Elipe, J.P.Espin6s, J.C.Conesa, J.Soria and J.Sanz, J.Phys.Chem.,_91 (1987) 6625. A.R.Gonz~ilez-Elipe, P.Malet, J.P.Espinfs, A.Caballero and G.Munuera, Stud.Surf. Sci. and Catal. 30 (1989) 427. Chapman & Hall (eds.) Dictionary of Inorganic Compounds, London 1984 (and references therein) S. Bernal, J.J. Calvino, G.A. Cifredo, J.M. Gatica, J.A. Perez-Omil and J.M. Pintado, JCS Faraday Trans. 89 (1993) 3499. D.E. Aspnes and A. Heller, J. Phys. Chem. 87 (1883),4919 G.Mtmuera, A.R.Gonz~ilez-Elipe, A.Mufioz, A.Fem~,ndez, J.Soria, J.C.Conesa and J.Sanz Sensors and Actuators 18 (1989) 337. J.Conesa, J.Soria, J.M.Rojo, J.Sanz and G.Munuera Zeit Phys.Chem. 152 (1987) 83. R. Burch, S.E.Golunski and M.S. Spencer, Catalysis Letters 6 (1990), 152. A.M~loz, A.R.Gonz~ilez-Elipe, G.Munuera, J.P.Espinfs and V.Rives-Arnau. Spectrochimica Acta, Part A, (Molecular Espectroscopy) 43 (1987) 1599.

A. Frennet and J.-M. Bastin (Eds.) Catalysis and Automotive Pollution Control 111 Studies in Surface Science and Catalysis, Vol. 96 9 1995 Elsevier Science B.V. All rights reserved.

123

ENHANCEMENT

OF THE REACTION OF NITRIC OXIDE AND CARBON MONOXIDE BY HYDROGEN AND WATER OVER PLATINUM AND RHODIUM-CONTAINING CATALYSTS

R. D t ~ m p e l m a n n a, N . W . C a n t a a n d D.L. T r i m m b

~School of Chemistry, Macquarie University, Sydney NSW 2109, Australia bSchool of Chemical Engineering and Industrial Chemistry, University of New South Wales, Kensington NSW 2033, Australia ABSTRACT

The addition of hydrogen or water to a stoichiometric mixture of CO and NO over supported platinum and rhodium catalysts can significantly increase the conversion of both NO and CO. Theselectivity of NO reduction is also affected in a remarkable manner. With Pt/AI203 at 210~ for example, addition of"~900 ppm 1-12increases the NO conversion from 6% to 48% and that of CO from 5% to 33%. The nitrogen atom of NO is converted quite selectively to NH3 while the oxygen atom forms CO2 rather than water. Addition of ~1400 ppm water also enhances both CO and NO conversion over Pt/AI203 but N2 rather than NH3 is the favoured product. Hydrogen and water also produce significant rate enhancements with Rh/AI203 and Rh/CeO2/AI203but the product distributions are somewhat different from those with Pt/A1203. Possible reasons for the enhanced activities and the observed selectivities are discussed.

1.INTRODUCTION

There is considerable literature concerning catalysis of the NO + CO and NO + H2 reactions over Rh and Pt in various forms. A general conclusion is that the latter reaction is substantially faster than the former with Rh [1,2] and especially Pt [1-4] under equivalent conditions. With respect to NO removal, the presence of CO inhibits the NO + H2 reaction [1-6], see also [7]. Rather surprisingly there appears to be no definitive studies of the mixed NO, CO, 1-12reaction system [7] even though all three gases are simultaneously present in automobile exhaust gases.

124 There is also little detailed work on the effect of water on the catalysed reaction of CO with NO. One might expect any effects to arise via hydrogen formation through the water gas shitt reaction (WGSR) between CO and 1-120. However, appreciable formation of NH3 has been found with CO, NO and water mixtm-es under conditions of little or no WGS activity [8] which indicates that water can act in other ways. In this context it may be noted out that current promoters such as ceria are associated with a high WGS activity [9,10] and that water may also act as an reoxidant of reduced ceria [11] with hydrogen evolution [12]. Promotional effects by both hydrogen [13-15] and water [15] have been reported for the oxidation of CO by oxygen. The exact mechanism is unclear. The present work describes the effect of hydrogen and of water on the NO + CO reaction over Rh and Pt at temperatures typical for the warm-up phase of catalytic converters. The data obtained demonstrate pronounced effects on reaction rates and product distributions which have apparently not been reported both in previous laboratory studies of the binary systems (NO + CO and NO + 142) and when using simulated exhaust gas mixtures.

2.EXPERIMENTAL

Catalyst: The catalysts were prepared by incipient wetness of powdered A1203 (Condea alumina washeoat grade, surface area ~140mE/g) with aqueous H2PtCI6 and RhC13 solutions to yield nominal contents of 1 wt% Pt and 0.53% Rh (same molar content). The slurries were dried at 50~ under mild vacuum in a rotary evaporator, dried fitrther at 100~ overnight and subsequently calcined for 4 h at 500~ The eeria containing catalyst was prepared by first impregnating with a solution of Ce(NO3)3, followed by drying and calcination as above, and then impregnated with the rhodium salt. The resulting powders were pressed, crushed and a sieve fraction of 106-180 mm was used in subsequent experiments. The pretreatment consisted of a temperature programmed reduction (1% Hz/He, 9~ up to 500~ followed by 30 min equilibration with 2000 ppm of CO and NO at 500~ and cooling in CO/NO to reaction temperature. Reactor: The experiments were performed in a continuous flow tubular reactor (Pyrex, 8 mm OD, 5 mm ID). The catalyst sample was held by a plug of quartz wool on top of a thermoeouple. All gases and gas mixtures were of high purity grade and not fiuther pmified. Calibrated mass flow controllers assured the desired concentrations. Analysis: The analyses were performed on-line by infrared spectroscopy (IR) and mass spectrometry (MS). The former method used a dispersive infrared spectrometer (Perkin-Elmer 580B) with a multiple path cell (2.4m total path length) and a control

125 computer. A routine was developed by which the absorbances of CO (2117 cml), NO (1877 crnl), N20 (1300 crn-1), NH3 (965 cm1) and CO2 (679 crn-1) were repeatedly acquired and stored on a cycle time of ~ 7 minutes. The mass spectrometer (VG300SX) was used for the detection of H~ (rn/e =2), CO2 (m/e =22) and NO (m/e =30). Signals at m/e =44 can stem from either N20 or CO2. Therefore, carbon dioxide was reliably measured by use of its doubly charged ion at m/e =22, which has a low background signal and is not interfered with N20 (no signal at m/e = 22 detected). In one instance (Figure 1) CO was also calculated from the MS signal at m/e =12 knowing the fragmentation patterns of CO and CO,. Formation of N2 and H~O were calculated by nitrogen and hydrogen balances. The gases CO, NO and N20 were calibrated through use of diluted standard mixtures. Known concentrations of CO~ and NH3 were obtained by passing CO and excess 02, or NO and excess H~, over the catalyst at 300~ In the latter case, concurrent nitrogen formation was measured by C~ analysis and the absence of N~O demonstrated by IR. Conditions: The catalyst weight was 75 mg and the flow rate 100 ml/min (STP) giving a GHSV of 50,000 h 1 (STP). The effect of addition of hydrogen and/or water on the reaction of CO and NO was determined under isothermal conditions. Each experiment was performed in the sequence a,b,c,d,a,c,b,d,a with a = only CO and NO, 2000 ppm each; b = a + ~ 890 ppm H2; c - a + ~ 1400 ppm (0.14%) H~O ; d = a + 900 ppm H2 and 1400 ppm H20. Steady-state reaction rates were obtained by nmning the corresponding experimental conditions for at least 21 minutes (3 IR analysis of the 5 gases) and taking the average of the last two measurements. Periods as long as one hour were required under some conditions to achieve a steady-state. The sequences were executed over several days at random temperatures in the range 190 - 290~

3.RESULTS 3.1 Example run Figure 1 provides an example of the changes in concentration observed during the first half of the standard sequence - in this case for reaction over Pt/A1203 at 290~ It should be noted that the data are not internally normalized, e.g. MS versus IR data, which would be impossible without some assumptions. The apparently negative N2 concentrations in some cases simply reflect the limits of analysis under conditions of small formation of N2. The conclusions which follow are based not solely on Figure 1 but on the examination of many data sets for a range of conditions. As shown in the top panel, introduction of H2 (a --~ b) induces a drop in NO signal (i.e. enhanced NO conversion) and an increase in CO2 formation as detennined by both MS and IR. Thus CO conversion has increased as well. Substitution of H2 by

126 1-120 (19 ~ c) gives ~ 2000 ppm CO~ (i.e. complete CO conversion) and the NO signal drops to zero. Addition of both Hz and 1-120 (c ~ d) gives a similar result while deletion of both (d ~ a) returns the concentrations close to the original values, after a delay. The subsequent a ~ c step results in similar steady state concentrations to those seen alter the successive a ~ b ~ c steps. The distribution between the various nitrogen containing products (lower panel) is also interesting.

.

9

a0oo-

I !

a. .

I t,. I

1 I

! !

I

i ~.

c.

I

I

! !

I L

I

a.

I

I c. 11 ...

_ C-balance 2 0 0 0 -- ---'------'~----~--~" E e',a

.. 1000

i:"~ .

--

t,'-

~

,\

"1~'-.--

::'13 E! = - - ~

0 :;=

NO (MS) CO~, (MS) CO 2 (IR) C-balance

m

!i

'~r ~i"~

L,..

c:: e,o o

-~.....

I

0-750

500

250

I

--

'

I

.'

"i

II

,._.~ "o

,

t A.

\A.

I

'

"~176 \-/I

~' or/

-

;',

-o-N,

v-

mass

N.~ om (,or,,, balance

2~, A. ~ using IR-data)

9 A. &

I

13

o~

9

,B' V V _ / 0 - x 3

m

; O-O

_o

v-- ~'v'

-

--

I

0 0%

I

14

Time

I [hours]

15

"~,,

'

16

Fig. 1 Concentration changes upon addition of H2 and~or H20 using Pt/Al203at 2~'~C. a =2000tTrn CO+NO, b.= a +890tlxn H~ c = a +1 4 0 0 ~ H20, d= a +H2+H20 Ammonia is dominant when hydrogen alone is included (b) whereas nitrogen dominates on addition of water alone (r Both NH3 and N2 are formed when 142 and 1-120 are included together (d). It should be noted here that the quantifies of NH3

127 detected (~ 540 ppm) are sufficient to account for most of the 890 ppm of H2 added. Conversely, very tittle hydrogen can be converted to water (< 60 ppm by H balance). The total carbon balance traces in the top panel reveal interesting transient effects. Addition of water (b --> e or a --> e) results in periods during which the carbon balance is in excess of the input quantity (2000 ppm). This indicates that a surface species has been reacted to produce carbon dioxide. Peaks in ammonia evolution occur over the same periods and the calculated N2 concentrations are then strongly negative as expected if the quantifies of NH3 (plus N20) being produced exceed that expected from the NO conversion. Deletion of water (d --> a) is followed by a period of deficient carbon balance (i.e. uptake to form a surface species). The significance of these transient effects is commented upon later. It should be stressed here that both the steady state concentrations and the transient effects were quite reproducible in response to other step-changes in the input concentration in the remainder of the standard sequence (i.e. e --> b --> d --->a). 3.2 Effects of temperature Similar sequences of experiments to those illustrated in Figure 1 were carried out at other temperatures and with the Rh/A1203and Rh/CeO2//0203 catalyst. Figure 2 shows concentration versus temperature plots extracted from the data set. The method of data collection results in some scatter (since determinations at different temperatures may be long separated in time) but minimises bias (since measurements with different compositions at the same temperature are close in time). The following conclusions may be drawn 1. With Pt/A1203 inclusion of H2 and/or H20 greatly enhances CO2 production (i.e. CO conversions) at all temperature (top panel, left). The enhancement by H2 exceeds that by H20 below 250~ but the reverse is true at higher temperatures. A similar pattern of enhanced CO conversion is evident with Rh/A1203 (top panel, fight) but its extent is less pronounced because of the higher intrinsic activity of rhodium for the reaction of CO with NO. 2. The principal nitrogen-containing product over Pt/A1,O3 when H2 is added is ammonia (second panel, left). However enhancement by water occurs largely with nitrogen formation (third panel, left). There is moderate N20 formation under all conditions (bottom panel left) and it is the most important nitrogen containing product for the reaction of CO and NO alone. 3. With Rh/A1203 enhancement by H2 (or by H2 and H,O together) gives more N,O than NH3 or N2 at the lowest temperatures but the relative amounts of each tend to equalise in terms of nitrogen content above 240~ As with Pt/A1,O3 nitrogen is the favoured product when water alone is added (third panel, right). Experiments with a catalyst containing 6% ceria (Rh/CeOJA1203), not shown, exhibit similar responses to the addition of H2 and H,O as the undoped Rh/A1,O3.

128

PtJAI203 9"

0001.I 8,1

'

"

t '-

'

-

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E o= ~

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.. IN=O~ (

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270 290 190 Temperature [ ~

/

210

,,

I

230

250

Figure 2. Product concentrations as a function of temperature for reactions of: (~----) CO + NO (2000 ppm each) (---x ..... ) CO + NO + H20 (1400 ppm) (-......= ........) CO + NO + H 2 (890 ppm)

(~O----)

CO + NO + H 2 + H20

\

,,,

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270

.

129 Differences in activity and selectivity between the two catalysts were also minor indicating that eeria has little effect on reaction characteristics under the conditions used here.

4.DISCUSSION Tables 1 and 2 summarise the most striking findings of the present work for the effect of H2 and HzO on the reaction of CO and NO. With Pt/A1203 at 210~ addition of hydrogen (Table 1) increases the conversion of NO by a factor of eight and that of CO similarly. Hydrogen conversion is close to complete. Over 90% of this hydrogen reacts with the nitrogen atom of NO to form ammonia, the dominant nitrogencontaining product, rather than with the oxygen atom to give water. Conversely the oxygen from NO is converted to CO2 with very high selectivity. In stoichiometric terms the reaction can be represented as CO + NO + 1.5H2

CO2 + NH3

(1)

At the same temperature, hydrogen enhances NO conversion over Rh/AlzO3 to a similar extent. However the conversion of 1-12is incomplete and the reaction tends to produce less ammonia and more NzO and N2. As a result the NO conversion is increased to a greater extent than the CO conversion. The increase in CO conversion on hydrogen admission appears very peculiar and to our knowledge has not been reported previously. Assuming that the reaction of NO proceeds by dissociation of adsorbed NO on vacant sites (*) i.e. *NO + * ~ * N + * O

(2)

then the adsorbed oxygen is seen to prefer to react with adsorbed carbon monoxide to form carbon dioxide O* + *CO ~

CO2 + 2*

(3)

rather than with hydrogen to form water O* + H* --~ *OH + * 9O H + H* ~ 1-120 + 2*

(4a) (4b)

The most probable explanation is that steps (3), (4a) and (4b) are all fast but that the quantity of adsorbed CO is much greater than that of hydrogen. As a result, the probability of an individual O* reacting according to (3) is very high. This is similar

130 to the situation prevailing during the reaction of CO/HJO2 mixtures on platinum group metals [13,14] where it is possible selectively to oxidise CO in a large excess of H2 because the former predominates on the metal surface. There is no simple explanation for the enhanced NO conversion observed when hydrogen is present. Step (2) above is generally thought to be the initial step [16,17]. It seems tmlikely that hydrogen could act by removing adsorbed O since the concentration of this species is believed small due to its efficient removal by reaction with adsorbed CO. In any case this reaction should lead to water which is not the favoured hydrogen containing product. Removal of adsorbed N to form ammonia (as observed) with creation of vacant sites could increase the rate of reaction (2) but only in situations where the nitrogen coverage was relatively high. This is just conceivable with rhodium [7] but is most tmlikely with platinum where a very large fraction of the surface is occupied by carbon monoxide [ 17,18]. However, removal of either adsorbed O or N by hydrogen may lead only temporarily to a large increase in vacant sites, because thus sites would be rapidly occupied by CO. A different situation arises if the removal of N or O itself is rate detennining, which seems rather unlikely. Another possibility is that NO dissociation is "hydrogen assisted' as proposed by Hecker and Bell [19] for the reaction between NO and 1-12i.e. *NO + H* ~

*N + *OH

(5)

Table 1 Enhancement by hydrogen Catalyst Inlet composition (temperature)

Conversion

(%)

NO

CO

Selectivities (%) of underlined atoms to NI-I~ a C0__2 N_N2 r NI-'I3 d b

Pt/A1203 210~

2000 ppm CO + NO + 890 ppm HE

6 47

5 33

97

100 96

e 0

75

Rh/ml203

2000 ppm CO + NO + 890 ppm H2

16 69

12 35

82

100 89

44 45

13

210~

a selectivity of the hydrogen atom, H ~ NH3 = 3 N H 3 / ( H 2 consumed) b selectivity of the oxygen atom, N(O) ~ CO2 = CO2/(NO consumed - N20 formed) selectivity of the nitrogen atom, (N)O ~ N2 = 1-(NH3+2N20)/(NO consumed) d selectivity of the nitrogen atom, (N)O ~ NH3 = NH3/(NO consumed) e not measured accurately at low conversions but N20 dominant

131 This path is favoured by recent theoretical calculations [20] which show that the activation energy is less than that for unassisted dissociation (reaction (2)) on both Pt (25 versus 54 kJ/mol) and Rh (13 versus 29 kJ/mol). An apparent problem with step (5) in CO/NO/H, mixtt~es is that it produces OH which one might expect to react to form water which is a minor product especially with Pt. A rapid reaction between CO and OH, or between water and support-bound isocyanate species as discussed later, would be required to produce CO2. "Hydrogen assisted' NO dissociation could also proceed via *NO + H* ~

*NH + *O

(6)

Although high activation energies were calculated for this reaction 20 (Pt: 96 kJ/mol, Rh: 67 kJ/mol) it would produce directly the adsorbed oxygen required for reaction with CO (3). In recent discussions on the NO + HE reaction Hirano et al. [7] found no experimental support for hydrogen assisted dissociation of NO. They argued, as an alternative, that NO dissociation requires empty sites adjacent to adsorbed NO molecules and that hydrogen could replace some weakly bound NO. They thought that this might provide additional sites for dissociation because of the small size of hydrogen. In summary there are a variety of possible explanations for the rate enhancement caused by hydrogen but none are very convincing with the current state of knowledge. Table 2 Enhancement by water

Catalyst (temperature)

Inlet composition

Conversion (%) NO

CO

Selectivities ~ (%) of N-atom of NO to

N2

N20 b

NH3

Pt/A1203 290~

2000 ppm CO + NO + 1400 ppm H20

24 98

21 100

c

83 r

-

77

10

12

Rh/A1203 270~

2000 ppm CO + NO + 1400 ppm H20

100 100

75 100

69 98

30 1

2

a for

N2 and NH3 defined as in Table 1 N 2 0 = 2N20/(NO consumed) not measured accurately, but selectivity to N20 is at least 83%

b (N)O ~

Water can enhance the reaction of CO with NO to a similar extent as shown in Table 2. The effects are apparent at somewhat higher temperatures and are again

132 more pronounced with Pt/A1203 than with Rh/AI203. It is most unlikely that the promotion arises through the water gas shift reaction since this would produce hydrogen and large amounts of ammonia would then be expected on the basis of the results in Table 1. Experimentally very little ammonia is observed using Pt/AI203 at temperatures above 270~ Nitrogen is the dominant nitrogen-containing species and the main reaction during water promotion can be represented simply as 2CO + 2NO ~ N, + 2CO2

(7)

With Rh/A1,O3 the principal effect of water is to favour nitrogen production at the expense of nitrous oxide CO + 2NO ~

CO2 + NzO

(8)

CO conversion is increased as a result of either reaction (7) or (8). The formation of nitrogen over Pt and Rh catalysts at temperatures below 327 ~ is now thought to proceed via a surface N20 intermediate under conditions where there are vacant sites [21 ]. It is difficult to see how this could be accelerated by water. One faint possibility was suggested by Muraki et al. [15] to explain water promotion of the reaction between CO and 02 on platinum catalysts. They suggested that water adsorbed in competition with carbon monoxide in such a way as to reduce the strong inhibitory effects present when carbon monoxide coverages are very high. It is difficult to see how this is possible given that the heat of adsorption of CO on Pt(111) for example, (134 kJ/mol) is very much greater than that of H,O (46 kJ/mol) [20]. The heat of adsorption of CO falls very steeply at high coverages (which might allow competition) but even then it is hard to see how this would increase the number of vacant sites as required to increase the rate of NO dissociation, reaction (2). Alternative explanations assuming that reaction is confined to the metal would require the supposition of'catalytic cycles' such as H20 *NO *N *N20 *CO

+ + + + +

2* ~ *H ~ *NO ~ *H ~ *OH~

*OH N* *N20 N2 CO2

+ +

H* *OH

+ +

*OH+ * H* + *

(9a) (9b) (9e) (9d) (9e)

in which a small quantity of adsorbing water results in the dissociation of many NO molecules. Reaction (9e) would need to be fast to prevent buildup of *OH. Recent calculations [22] indicate that the activation energy for reaction (9e) is low on platinum group metals (e.g. 4kJ/mol for Pd). While this cycle is very speculative, it

133

can account for some of the differences between 1-12and 1-120promotion. Dissociation of water according to reaction (9a) would be slower than hydrogen dissociation necessitating a higher temperature, as observed experimentally. As a consequence the concentrations of adsorbed H and OH would be lower because of faster removal by reactions (9b), (9d) and (9e), leading to low ammonia formation - again as observed. A final possibility which warrants mention is the potential involvement of isocyanates (NCO) as intermediates. Such species are very unstable on platinum group metals [23] but their spillover to supports is well documented [24]. Support bound isocyanates react readily with water even at room temperature to give ammonia and carbon dioxide [24]. Some evidence for the presence of NCO and their diffusion to the support is provided by the carbon balance and NH3 traces in Figure 1. The periods of "excess' carbon and ammonia evolution after water introduction are equivalent to about 30 mmol. For comparison the total quantity of Pt is 3.9 mmol and the number of support sites is 150 mmol (assuming 1019 sites/m2). Thus the data is consistent with the view that roughly 20% of the alumina surface is covered by isocyanate groups which are hydrolysed to NH3 and CO, on introduction of water. The corresponding periods of carbon deficit observed on deletion of water are almost step changes, indicating that the spillover and transport processes required to refill empty sites are quite fast at 290~ It is unlikely that hydrolysis of isocyanates is a major product route under steady state conditions with water present since little ammonia is formed. The process could act as a way of converting water to ammonia during enhancement by hydrogen but more direct experimental methods, such as infrared spectroscopy, are needed to evaluate this possibility.

5.CONCLUSIONS

1. Hydrogen enhances the rate of the reaction of CO and NO on alumina supported platinum and rhodium. The major pathway involves combination of hydrogen with the nitrogen of NO to form ammonia while the oxygen released is taken up by CO. 2. Water promotes the reaction of CO with NO. It does not seem to participate directly in the reaction but affects the characteristics of the reaction in a way which favours nitrogen production. 3. A variety of explanations can be advanced to explain the effects of hydrogen and water but none are very convincing given current knowledge. 4. Support bound isocyanate species may be involved in transient effects seen when water is introduced and subsequently deleted.

134

ACKNOWLEDGMENT

This work was supported by a grant from the Australian Research Council. The financial support of the Swiss National Foundation for one of the authors (R.D.) is gratefi~y acknowledged. REFERENCES

8

9 10 11 12 13 14 15 16 17 18 19 20 21 22 23

T.P. Kobylinski and B.W. Taylor, J. Catal., 33 (1974) 376. H. Shinjoh, H. Muraki and Y. Fujitani, Stud.Surf.Sci.Catal., 30 (1987) 187. K.C. Taylor and R.L. Klimisch, J. Catal., 30 (1973) 478. M. Shelefand H.S. Gandhi, Ind. Eng. Chem. Prod. Res. Develop., 11 (1972) 393. J.H. Jones, J.T. Kummer, K. Otto, M. Shelef and E.E. Weaver, Env. Sci.Technol., 5 (1971) 790. L. Heezen, V.N. Kilian, R.F. van Slooten, R.M. Wolf and B.E. Niewenhuys, Stud.Surf.Sci.Catal. 30, (1987) 381. H. Hirano, T. Yamada, K.I. Tanaka, J. Siera and B.E. Nieuwenhuys, in: New Frontiers m Catalysis, Guczi et al. (eds.), Proc. 10th Int. Congress on Catalysis, Elsevier, (1993) 345, see also the included Question/Answer section. M.L. Unland, J. Phys. Chem., 77 (1973) 1952. G. Kim, Ind. Eng. Chem. Prod. Res. Dev., 21 (1982) 267. B. Harrison, A.F. Diwell and C. Hallett, Platinum Metals Rev., 32 (1988) 73. R.K. Herz, Ind. Eng. Chem. Prod. Res. Dev., 20 (1981) 451. C. Padeste, N.W. Cant and D.L. Tfimm, Catal. Lett., 18 (1993) 305. S.E. Oh and R.M. Sinkevitch, J. Catal., 142 (1993) 254. J.R. Stetter and K.F. Blurton, Ind. Eng. Chem. Prod. Res. Dev. 19 (1980) 214. H. Muraki, S. Matunaga, H. Shinjoh, M.S. Wainwright and D.L. Tfimm, J.Chem. Tech. Biotechnol., 52 (1991) 415. B.E. Nieuwenhuys, Surf. Sci., 126 (1983) 307. R.M. Lambert and C.M. Comrie, Surf. Sci., 46 (1974) 61. R.F. van Slooten and B.E. Nieuwenhuys, J. Catal., 122 (1990) 429 W.C. Hecker and A.T. Bell, J. Catal., 92 (1985) 247. E. Shustorovich and A.T. Bell, Surf. Sci., 289 (1993) 127. H. Hirano, T. Yamada, K.I. Tanaka, J. Siera, P. Cobden and B.E Nieuwenhuys, Surf. Sci., 262 (1992) 97. E. Shustorovich and A.T. Bell, Surf. Sci., 253 (1993) 386. J. Rask6 and F. Solymosi, J. Catal., 71 (1981) 219. F. Solymosi,L. V61gyesiand J. Rask6,Z. Phys. Chemie (Neue Folge), 120 (1980) 79.

135 24 25 26 27 28 29 30 31 32

M.L. Unland, J.Catal., 31 (1973) 459. R.J.H. Voorhoeve and L.E. Trimble, J.Catal., 54 (1978) 269. D.A. Lorimer and A.T. Bell, J.Catal., 59 (1979) 223. M. Shelef and H.S. Gandhi, Ind.Eng.Chem.Prod.Res.Develop., 13 (1974) 80. W.F. Egelhoff, in: The chemical physics of solid surfaces and heterogeneous catalysis, D.A. King and D.P. Woodn~(Eds.), Elsevier, Vol. 4 (1982) 397. J.J. Jones, J.T. Kummer, K. Otto, M. Shelef and E.E. Weaver, Env.Seienee & Teeh. 5 (1971) 790.. H. Shinjoh, H. Muraki and Y. Fujitani, in: Catalysis and Automotive Pollution Control, A. Crueq and A. Frennet (Eds.), Elsevier, 187 (1987). L. Heezen, V.N. Kilian, R.F. van Slooten, R.M. Wolf and B.E. Niewenhuys, in: Catalysis and Automotive Pollution Control, A. Crueq and A. Frennet (Eds.), Elsevier, 381 (1987). Y. Amenomiyaand T. Tagawa, 8th Proe.Int.Cong.Ca_ta!.,Bedin,Vol. 2 (1984) 557.



137

SIMULTANEOUS NOx REDUCTION AND SOOT ELIMINATION FROM DIESEL EXHAUST ON PEROVSKITE-TYPE OXIDE CATALYSTS V. Duriez, L. M o n c e a u x and P. C o u r t i n e

Division Physico-chimie et Analyse des Procddds Industriels, Universitd de Technologie de Compikgne, B.P. 649, 60206 COMPIEGNE Cddex, France

ABSTRACT

Series of partially substituted manganates belonging to perovskite structure family is prepared and characterized with a view to use them as catalyst for reduction of nitric oxides with carbon black. Catalytic tests show that the series Lao.8Sr0.2Mnl-xCuxO3+l have the best activity among the perovskite samples. La2CuO4, which belongs to K2NiF4 structure family, is more active than the others, but unfortunately under test conditions it is partially reduced into La203 and CuO. Some interpretation of the high activity of these phases are given, based on intrinsic properties of the studied phases.

1 INTRODUCTION In gasoline engine exhaust gas, the nitrogen oxides are eliminated with the help of carbon monoxide which is present in sufficient proportion. The composition of diesel exhaust gas is, on the contrary, low in CO and high in oxygen, and contains soot particulates. In the present work, an attempt is made to study the feasibility of using soot particulates as a reducing agent of NO. For this purpose, to simplify the system, soot is simulated by carbon black and the gas phase is exclusively composed of nitrogen and NO. Various substituted lanthanum manganates having the perovskite ABO3type structure, as well as La2CuO4 and simple copper oxides are studied. In the present study, are reported the synthesis, characterization of the various phases and catalytic test results.

138

2.EXPERIMENTAL 2.1.Catalyst preparation

A series of lanthanum, partially substituted by strontium or cerium, manganese perovskites are synthetized. Some of them are also substituted by noble metals ~ and/or Pd) or by copper in B-site. To improve homogeneity and to lower the phase formation temperature, a sol-gel process is used for the synthesis. Citric acid, rare earth nitrates, other metal nitrates (or acetates for copper compounds), and, when necessary, hexachloroplatinic acid in the required proportions are dissolved in ethylene glycol. After complete dissolution under energetic and constant stirring, the gel is formed by heating slowly. Then, it is transferred into a porcelain dish and again heated to obtain a black solid which is slowly fired in a muffle furnace under air from room temperature to 600~ (5~ and afterwards maimained at 600~ during 6 hrs. Cerium containing samples are heated at 600~ during 6 hrs, then 800~ during 4 hrs and 900~ during 4 hrs, and samples of the series La0.8Sr0.2Mnl-xCuxO3+l are calcined at 600~ (6 hrs), then 700~ (6 hrs) and 900~ (4 hrs). La2CuO4 sample has been prepared differently. Lanthanum nitrate and copper acetate in stoichiometric quantity are dissolved in water. Then the solution is evaporated under vacuum by heating at 60-70~ until a gel is obtained. After desiccation the precursor is heated slowly under air (5~ to 300~ and maintained at this temperature during 3 hours and then calcined at 800~ during 5 hours. Before testing the powder is carefully ground with carbon black (10 wt %) and then compacted into pellets (3 mm diameter and height).

2.2.Characterization

X-Ray diffraction

X-Ray difflaction experiments (XRD) are perfonned on a curve position sensitive detector INEL CPS 120 which allows a simultaneous collection of diffracted beams in the range 5 ~ < 2 0 < 125 ~ with the monochromatized CuKal radiation. Powder samples are manually compacted on windowed aluminum holders. After typically one hour of accumulation, patterns are analyzed with the DIFFAC-AT Siemens software program, a-alumina is used as an internal standard.

139

Specific area Specific area measurements are performed with a "Quantasorb Jr." apparatus by N2 adsorption in liquid nitrogen temperatm'e (standard multipoint BET method).

Manganese valency measurement To determine manganese valency, the method previously described by Bloom et al. [1 ] is employed. As it uses the ability of Fe 2+ ions to reduce Mn3+ and Mn4+ in Mn2+ ions, it may not be employed for cerium and copper containing compounds as long as the valencies of these ions in the sample are not determined. Owing to the determination of Mn4+ content it is then possible, using electrical neutrality equations, to find the value of the non-stoichiometry in oxygen 1.

2.3.Catalytic Test

Experimental set-up The catalytic activity is tested in a vertical fixed bed reactor made of stainless steel and placed in a tubular furnace. 2 cm 3 of pellets composed with a mixture of carbon black (10 wt %) and catalyst are placed in the reactor. To clean the catalyst and carbon black surfaces the pellets are pre-treated by heating at 300~ during 1.5 hr under nitrogen. Then during the cooling of the solid to ambient temperature, a gas mixture containing 1020 ppm of NO in nitrogen is prepared in the by-pass circuit. As soon as the gas stoichiometry is well stabilized it is allowed to flow through the reactor which is heated from ambient temperature to 500~ at 4~ then the temperature is kept constant during 12 hours. The total gas flow rate is 50 1/~ (VVH = 25,000 hr-1), each flow rate being adjusted by means of massic flow rate controllers. Gas composition is continuously measured on-line by various analyzers : CO2 and CO contents are determined by IR absorption, NO or NOx by chemiluminescence. N20 is not measured but oxygen balances allow us to think that N20 may not be formed in quantity above 100 ppm. 3.RESULTS

3.1.Characterization Results of characterization are given in Table 1. X-ray analysis shows that in all cases (except La2CuO4, CuO and Cu20), a perovskite type phase is formed

140 with CeO2 for cerium containing phase and SrCO3 (traces) for B-site substituted compounds. For the series La0.8Sro.2Mnl-xCuxO3+~,, it is important to note that LazCuO4 appears only for 0.4 --- x -< 0.6. The highest content in La2CuO4 is found for x = 0.6. Nevertheless, measurement of relative intensities of the most important XRD peaks in La2CuO4 and the perovskite shows that the concentration in La2CuO4 must not be more than 9 %. On an other hand, for x 3 0.7 the perovskite (without any trace of La2CuO4) crystallises in the orthorhombie system whereas all the others may be indiced in the hexagonal system. La2CuO4 is synthetized as a single phase. Its structure is derived from the perovskite one and known as KzNiF4 structure [2]. It may be considered to be built up of alternating layers of perovskite (ABO3) and rock salt (AO) structures [3]. These compounds, as for perovskite oxides, may accept ions in substitution and have a certain degree of non-stoichiometry. A tolerance factor, comparable to Goldschmitt tolerance factor for perovskite, has been defined for K2NiF4 structure and it must be noted that the one of La2CuO4 is very close to the upper limit [2]. Concerning the determination of Mn4+ content and the evaluation of the non-stoiehiometry in oxygen our results for the two first compounds of Table 1 are in perfect accordance with those of Takeda et al. [4] who have also found that the introduction of a deficiency in A cation leads to a decrease in oxygen stoiehiometry, whereas the Mn4+ content remains constant. This may be explained by the increase in cationic vacancies. In the same way, the lack of B cation leading to an enhancement in Mn4+ content and at the same time to a very important decrease in oxygen stoiehiometry, may only be understandable by the formation of cationic vacancies. Lanthanum substitution by strontium has been widely used to improve catalytic performance [5-7] arguing the increase in Mn 4+ content for charge compensation. In fact, the determination by titration of Mn4+ content shows, on the opposite, a decrease in Mn4+ content accompanied by a decrease in oxygen stoichiometry. This is in accordance with the results of Kuo et al. [8] who determined oxygen stoichoimetry by TGA measurements as well as other works based on Mn4+ titration [9, 10].

141

Table 1 Catalysts characterization

Structure

Specific area (m2/g)

Mn 4+

(%)

LaMnO3•

P

20.6

46

0.23

La0.8Sr0.2MnO3+E

P

15.9

36

0.08

La0.900.1MnO3+~,

P

19.2

46

0.08

La0.9Ce00.. 1MnO3+E *

P + eCeO2

8.9

La0.8 Sr0.2Mn0.900.103+~,

P + eSrCO3

26.65

55

- 0.03

La0.8 Sr0.2Mn0.999Pt0.00103•

P + 8SRCO3

22 4

42

0.11

La0.8 Sr0.2Mn0.999Pd0.00103•

P + eSrCO3

23 0

50

0.15

La0.8 Sr0.2Mn0.998Pt0.001Pd0.00103•

P + eSrCO3

22.3

50

0.15

La0.8 Sr0.2Mn0.9Cu0.103•

**

P

6.2

La0.8Sr0.2Mn0.8Cu0.203•

**

P

5.2

La0.8Sr0.2Mn0.7Cu0.303+~ **

P

5.0

La0.8 Sr0.2Mn0.6Cu0.403•

**

P + cLa2CuO4

4.2

La0.8 Sr0.2Mn0.5Cu0.503•

**

P + eLa2CuO4

4.7

P + eLa2CuO4 p,

3.02

p,

1.5

p,

1.8

p,

0.6

K2NiF4

0.83

CuO

CuO

4.3

Cu20

Cu20

0.8

La0.8Sr2Mn0.4Cu0.603• La0.8Sr0.2Mn0.3 Cu0.703•

** **

La0.8 Sr0.2Mn0.2Cu0.803+~, ** La0.8Sr0.2Mn0.1Cu0.903• La0.8Sr0.2CuO3•

**

**

La2CuO4**

* T ~ calcination : 600~ (6 h), 800~ (4 h), 900~ (4 h) ** T ~ calcination : 600~ (6 h), 700~ (6 h), 900~ (4 h) P : perovskite structure, hexgonal system P' : perovskite structure, orthorombic system

2.2

142 The introduction of noble metal in B-site substitution does not have any influence on oxygen stoichiometry.

3.2.Catalytic Activity First of all, in order to evaluate the specific contribution to the reaction of the catalyst on the one hand, and the carbon black on the other hand, experiments are performed either with catalyst and without carbon black or with carbon black in silica as an inert material. In both cases there is no conversion of NO. On the opposite, if catalyst and carbon black are both present, the evolution of the composition of the exhaust gas shows that there is effectively an oxidation of carbon black into CO2 accompanied by NO reduction. On Figure 1, are represented typical curves showing the variation of NO and CO2 concentration as a function of time and temperature. These curves are divided into three main parts. In the first zone (zone A) there is an important drop of NO concentration due to the entering of the gas flow through the reactor and to NO adsorption. The second part (zone B) corresponds to NO desorption due to the temperature increase, with two main peaks : one around 170~ and the other around 350~ the exact value depending on the type of catalyst. These desorption peaks are not apparent on La2CuO4 curve because of its low specific area. It must be noticed that CO2 production begins generally during the first part of this second peak and this is the real beginning of the reaction between NO and C. In all experiments, no CO has been detected. In the third zone (zone C), NO concentration drops more or less drastically and, jointly, CO2 concentration increases. Then, as the carbon black is consumed and as there are more and more diffusion phenomena inside the pellets, deNOx reaction, though being still effective, is less important. For all the experiments, oxygen balance has been verified and the reproducibility of the results is about 5 %. In order to compare the various catalysts it is necessary to take into account the catalyst specific area and the amount of carbon black introduced as the pellets are not always compacted exactly alike. Therefore, the activity is given as the number of moles of NO converted per unit of surface of catalyst and unit of mass of the solid mixtm'e (catalyst + carbon black). Results are given in Table 2.

4.DISCUSSION Results of the catalytic tests show that it is possible to reduce NO with the help of carbon black. NO is probably adsorbed on the surface of the catalyst and

143 then either just aider desorption, or as it is still adsorbed, it reacts with carbon black to give CO2 and N2. The exact mechanism is still not completely understood. The activity of LaMnO3 is very low compared to all the other studied catalysts, and it does not seem to be directly connected with the Mn4+ content contrarily to what was established for the reduction of NO by CO [11 ]. On the opposite, the results confirm the benefic effect of substitution, particularly in Asite (Sr or O) which may be explained by the modification of the binding energies A-O. As Voorhoeve has shown for the reduction of NO by CO, the progression of the activity follows the order : LaMnO3 < LaOMnO3 < LaSrMnO3.

Table 2 Catalytic activity of the tested catalysts Activity* x 104

Catalyst

Activity* x 104

LaMn03

0.29

Lao. 8Sro.2Mno. 9Cuo. 103

2.89

Lao.8Sro.2Mn03

1.30

Lao. 8Sro.2Mno. 8Cuo.203

3.66

Lao.90o. 1Mn03

0.65


2.88

Lao.9Ceo. 1Mn03

0.40

Lao. 8Sro.2Mno. 6Cu0.403

1.99

Lao. 8Sro.2Mno.90o. 103

0.74


6.84

Lao. 8Sro.2Mno. 999Pto.oo 103

1.70

Lao.sSro.2Mno.4Cuo.603

2.91

Lao. 8Sro.2Mno. 999Pdo.oo 103

2.36

Lao.8Sro.2Mno.3Cuo.703

2.38

La0.8 Sro.2Mno. 998Pt0.oo 1Pdo.oo 10~ 2.54

Lao. 8Sro.2Mno. 2Cuo. 803

4.39

Lao. 8Sro.2Mno. 1Cu0.903

1.82

La0.sSro.2CuO3

2.82

Catalyst

* (moles NO converted/m2.g)

La2CuO4

30.4

CuO

18.43

Cu20

0.17

144

"• &

oc U

1 000

~

, , La0.sSr0.2MnO3+_x . . . . . . . . . . . . . . .

R 750

750

500

500

250

250

i00

200

300

400

500

Time E 1 000 & o "~

1 000

900 (min)

10o0 A , B ~.~

C

v

/----

750

750

I,.,

K o

500

500

"-' >., u~

,-.9

250 C0:, _

__

~

i O0

200

I,

~

300

400

~ / /

u

1 000

U

9

500

900

(m.i.n)

La2CuO4

A

c ,~9

C~

/A--.---

Time E 1 000 &

250

I

i

750

750

f

NOx 500

-

500

.t.-

0

U

250

250

COp. !

100

200

300

400

_

9

If:

l

500 900

Time (mEn)

Figure 1. Evolution of N O x and CO2 concentrations (. . . . inlet NOx)

U

145 When very little quantities of noble metals (Pt, Pd) are added, the activity is again increased. This may be related to the work of Johnson et al [12] who observed an enhancement of the activity of platinum when inserted into the perovskite matrix for the reaction of oxidation of CO. However, as noble metals are introduced in a very low proportion, no modification of the XRD patterns showing the insertion of Pd or Pt in the perovskite lattice can be evidenced. On the opposite, using SEM observations, no cluster of palladium or platinum is detected ; therefore, to be really sure that the noble metals are in the lattice, more investigations are needed. The second series of tested compotmds are the copper containing phases 9 Lao.8Sr0.2Mnl-xCuxO3+;~ (0_<x___l), La2CuO4 and simple copper oxides : CuO and Cu20. Theses phases are tested under the same conditions in order to try to evidence the influence of the host matrix on the activity and stability of copper. Concerning the stability, it is important to note that perovskite compounds are the only ones the structure of which remains unchanged under operating conditions. On the contrary XRD analysis of the samples after test shows that La2CuO4 decomposes into a mixture of La2CuO4, La203 and CuO, that CuO is partially reduced in Cu20 and at last Cu20 is also partially reduced in metallic copper. It seems, therefore, that the insertion of copper in the perovskite lattice leads to a certain stabilization as it was already reported in literature for LaMnl-xCuxO3• compounds [ 13]. Lao.8Sro.2Mnl-xCuxO3+~, and La2CuO4 phases are more active for the studied reaction than copper free perovskite and therefore copper seems to play a very important role. This may be explained by the fact that in the perovskite-type phase, the CuO6 octahedra are distorted due to Jahn-Teller effect, and therefore there are two longer Cu-O bonds, inducing a lower binding energy, and making possible the creation of oxygen vacancies which are often considered as being preferential adsorption sites of NO [ 14]. The evolution of the activity as a function of copper substitution is given on Figure 2 : the shape of the curve may be compared to the one obtained by Chan et al. [9] for the oxidation of CO over copper substituted lanthanum manganates although these authors tested neither x = 0.5 nor x > 0.8. For x = 0.5 there is a maximum in activity, which may be related to the maximum in NO adsorption as reported by Mizuno et al. [15].

146

Moles of NO/m2.g (x 104)

T

i

0.2

0.4

0.6

0.8

•

Figure 2. Activity of Lao.8Sro.2Mnl-xCuxO3:L2 as a function of copper substitution The highest activity is observed for La2CuO4. In this type of structure, copper ions are at the centre of distorted CuO 6 oetahedra as in perovskite phase, but the coordination number of lanthanum is 9 instead of 12. Kudo et al. [16] have also noted a high activity of this phase in the case of the reduction of NO with NH3. An explanation could be that the value of the tolerance factor t of La2CuO4 is very close to the upper limit of stability of K2NiF4 structure and therefore, to stabilize the compound in this structure copper ions are able to modify their ionic radii toward a more favourable value of t by disproportionation of Cu2+ in Cu + and Cu3+ or more probably by forming charge density waves [2]. CONCLUSION This study has shown the feasibility of catalytic NO reduction with carbon black, on various substituted rare earth transition metal oxides having perovskitetype structure or related structure (K2NiF4). The most active catalysts are those containing copper, particularly Lao.sSro.2Mno.sCuo.503 and La2CuO4. The origin of the very important activity of these phases may be found in the intrinsic properties of copper ion which is in the centre of a distorted octahedra with two weak Cu-O bonds. Therefore, oxygen vacancies, which are supposed to be preferential NO adsorption sites, may be easily created. Concerning La2CuO4,

147

the hypothesis of formation of charge density waves which has been reported by Ganguly may also enhance the activity. However, more investigations concerning NO adsorption, copper ion valency measurements and stability of the various phases are needed. Jointly, tests with partial pressure of oxygen are in progress.

REFERENCES

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16

E. Bloom Jr. and T.Y. Komenati, J. Inorg. Nucl. Chem., 40 (1978) 403-405. P.Ganguly and C.N.R. Rao, J. Sol. State Chem., 53 (1984) 193-216. D.Balz and K.Pleith, Z. Electrochem., 59 (1955) 545. Y. Takeda and S. Nakai, Mat. Res. Bull., 26 (1991) 153-162. T. Nitadori and S. Kurihara, J. Catal., 98 (1986) 221-228. R.J.H. Voorhoeve, Adv. Mat. Catal., (1977) 129-181. J.L.G. Fierro, Catal. Today, 8 (1990) 153-174. J.H. Kuo and H.U. Anderson, J. Sol. State Chem., 83 (1989) 52-60. K.S. Chan, J. Ma, S. Janicke and G.K. Chuah, Applied Cata. A, 107 (1994) 201-227. G.H. Jonker and J.H. van Stanten, Physica XVI, 3 (1950) 337-349. R.J.H. Voorhoeve, J.P. Remeika, L.E. Trimble, A.S. Cooper, F.J. Disalvo and P.K. Gallagher, J. Sol. State Chem., 14 (1975) 395. D.W. Johnson, P.K. Gallagher, G.K. Werther and E.M. Vogel, J. Catal., 48 (1977) 87-97. M.L. Rojas, J.L.G. Fierro and L.G. Tejuca, A.T. Bell, J. Catal., 124 (1990)41-51. Y. Teraoka and H. Fukuda, Chem. Lett., (1990) 1-4. N. Mizuno, Y. Fujiwara and M. Misono, J. Chem. Soc., Chem. Commun., (1989) 316-318. T.Kudo,T.GejoarflK. Yoshida,Am.Cho~Soc.,12(1978)n~


A. Frermet and J.-M. Bastin (Eds.) Catalys& and Automotive Pollution Control III Studies in Surface Science and Catalysis, Vol. 96 1995 Elsevier Science B.V.

149

HOW A THREE-WAY CATALYST IS A F F E C T E D UNDER TRANSIENT CONDITIONS : A STUDY OF Pt-Rh/Al203 CATALYST

C.Howitt, V.Pitchon, F.Garin and G.Maire LERCSI, Laboratoire d'Etudes de la R~activitd Catalytiques, des Surfaces et Interfaces, URA 1498 du CNRS- Institut le Bel, Universit~ Louis Pasteur, 4, rue Blaise Pascal, 67070 Strasbourg, FRANCE.

ABSTRACT

This publication describes results obtained for CO, NO and C3H8 conversion over alumina supported Pt/Rh, Pt and Rh catalysts operating under transient conditions. We show that, for the bimetallic catalyst, oxygen plays an important role in changing the surface composition. By performing activity testing experiments under cycling conditions and different gas mixtures, along with 'step-change' experiments, we suggest that, under fuel-rich and stoichiometric conditions, both Pt and Rh exist on the surface in a reduced state. However, under fuel-lean conditions, we show that Rh segregates from the Pt forming an inactive surface oxide, thought to be Rh203. It is shown that this redox process occurs within 10 seconds.

1. Introduction Since their introduction to production vehicles in 1975, a great deal of research has been undertaken to try to understand the reactions occuring over, and the mode of operation of, three-way automotive exhaust catalysts [1-3]. Since, under 'real' conditions, these catalysts never operate under steady-state conditions [4] one of the best ways to study the operation of these catalysts has been to use a system similar to that desigaled by Schlatter et al. [5,6], which facilitates the study of three-way responses to transient changes in gas composition. In recent years, numerous workers have studied the binary reactions CO + 02 and NO + CO over precious metal catalysts. However, whilst it is widely accepted that the reaction of CO and 02 proceeds via a Langmuir-Hinshelwood mechanism involving the reaction between adsorbed CO and O [7-9], and the

150 NO/CO reaction involves the adsorption/dissociation of NO [8,10-13], the literature is still unclear as to the state of the active surface of the catalyst [1416]. These binary reactions have been studied over Pt-Rh/SiO2 catalysts [17,18], different crystallographic faces [19] and using different teclmiques [20,21 ]. In all eases they show that some degree of surface reorganisation occurs during the reactions. When NO and 02 are in excess it has been suggested that Rh segregates from the Pt due to the high Rh-O bond strength compared to Pt-O, it is also shown that the catalyst surface behaves differently towards the NO/CO reaction than to the CO/O2 reaction [17,18]. This study uses low loaded A1203 supported Pt, Rh and Pt-Rh catalysts to study the reaction between NO, CO, O2 and C3H8 (HC) as a fifll gas mixture of varying composition, or any combination of oxidising and reducing gases (e.g. the reactions between CO + 02, NO + CO and NO + HC). The flexibility of the apparatus also allows the study of the response to so-called 'step-changes' in gas composition, described by H. and M. Kobayashi [22] and also in this laboratory by Weibel [23]. Thus, we present results which contribute sigafificantly to our understanding of the mode of operation of three-way automotive catalysts under transient conditions.

2. EXPERIMENTAL

2.1. Catalysts All of the catalysts used in this study were prepared by the Institut Fran~ais du Petrole (IFP) by impregnation of A1203 spheres (3 mm diaaneter), prior to testing the catalysts were crushed to obtain grains of diameter between 80 mad 250 [am. The metal loadings of the catalysts used are 1.1% Pt, 1.0% Rh for the monometallic and 1.1% Pt, 0.2% Rh for the bimetallic. 2.2. Catalytic measurements The experimental setup used for the catalytic tests was similar to that described by Schlatter et aL [5,6]. The system was designed such that the reaction gas streams could be as simple as binary mixtures, or as complex as the reaction between NO, CO, 02 and C3H8 (HC). By choosing the correct flow rate of each of the reactant gases, the gas composition could be varied thus allowing the catalytic activity to be studied under oxidising or reducing media with varying strengths, SN, defined by the following ratio : SN = (2 [02] + [NO]) /([CO] + 10 [C3H8])

151 The flexibility of the apparatus, and the accompanying 'home-made' software allowed two distinct types of experiment to be conducted, namely 'lightoff temperature' measurements under oscillating and steady-state conditions, and so called 'step-change' experiments [22,23], the details of each type of test shall now be described.

0 Light-off temperature measurements under oscillating conditions The aim of this test was to measure the light-off temperatures for NO, CO and HC conversions, while exposing the catalyst to a flow of gases oscillating between two compositions under a constant heating rate. The gas composition could be chosen so as to oscillate about stoichiometric (SN=I), reduchlg (SN1) media, with varying amplitudes. The frequency of switching between the two gas compositions, was also variable and was controlled by two fast actfiag solenoid selector valves located at the top of the reactor. The selector valves allowed the frequency to be varied between 0.05 and 1 Hz.

Testing Procedure A sample of the catalyst (100-400 rag) was placed in a straight silica reactor (10 mm i.d.), and mounted in the centre of a vertically held tube filmace. The point about which the reaction should oscillate was selected, along with the amplitude and frequency. The flow of gases was controlled by a series of eight mass flow controllers (Tylan FC260), and the switching was controlled by two solenoid selector valves (Burkert Type 330). The flow controllers, and the selector valves were driven by a 'home-made' computer program. The catalyst was heated to typically 450~ at a ramp rate of 4~ min-1 under a total gas flow of 200 cm 3 min-1, after which time the catalyst was cooled back to room temperature, this first rtm was to 'activate' the catalyst. After activation the experiment was repeated, it is from this second run that the results are taken. For analysis, CO, HC and CO2 were measured using infrared detectors, NO by chemiluminescence, and 0 2 by paramagaaetism.

ii) Step-change measurements for the C0/02 reaction The catalyst was initially stabilised under a reducing or oxidising stream under isothermal conditions. For the reduction step measurement, the catalyst was stabilised under oxidising conditions (i.e. 02) for a chosen length of time, after which the gas stream was switched to reducing conditions for a length of time, before being switched back to 02. During the oxidation step measurement the catalyst is stabilised under CO before being switched to 02, and then back to CO. Each transition was separated by a 15 minute pulse of N2 in order to remove

152

the gas phase, and to remove weakly held species from the surface of the catalyst. The transient response to the step-changes was measured by monitoring the instantaneous evolution of CO2 from the surface of the catalyst. For the step-change experiments, 400 mg of the Pt-Rh catalyst were used. The temperature was increased up to 300~ at a rate of 4~ min-1 under the appropriate pretreatment gas (CO or 02) at a flow rate of 200 cm3 rain-1. The times for which the catalysts were exposed to each gas are given as footnotes to the results tables; where, tl is the time for the pretreatment step, t2 is the oxidation/reduction step length, and tN is the time for which the system was purged in N2 prior to changing gases.

3. RESULTS AND DISCUSSION

3.1. Activity studies of the Pt-Rh/AI20 3 catalyst 0 Variations in activity with catalyst mass for the full mixture under oscillatory operation The activity of the system for CO, NO and HC conversion was measured using 100, 200 and 300 mg of the catalyst. Figure 1 shows typical variations in conversion with reaction temperature for CO, NO and HC. It is to be noted from this figure that in the NO profile a peak centred around 250~ is observed. This peak has been shown to be due to the formation of N20 arising from the partial reduction of NO. Typical results obtained from this series of experiments, along with the reaction conditions are given in Table 1. Normally, in the absence of diffi~sion limitations, we would expect the activity of a catalytic system to increase with increased catalyst mass, however, it can be seen from this Table that up to 50% conversion, no such correlation is observed. In order to investigate this phenomenon, it is necessary to study, in isolation, the simple binary reactions occurring in the fidl gas mixture. Table 1. Temperatures (~ for 50% conversion of CO, NO and HC over PtRh/AI203 a 100 mg 200 mg 300 mg CO

233

245

239

NO

299

330

342

HC 283 323 334 a Oscillating about SN=I, +/- 0.1 unit; f=0.05 Hz; Mean concentrations (ppm)" CO, 5600; NO, 2050; 02, 6000; HC,900.

153

'~176 l

801

!! CO

~ I

l!;

4o

"l

]/i

20 /

------

NO

. . . .

HC

] r~,J

o

50

100

150

200

250

300

350

400

450

500

Temperature/~

Figure 1 9Conversion vs. temperature for CO, NO, HC on Pt-Rh/Al20 3 under oscillatory operation (70 Variations in activity as a function o f mass for the bmary reactions The binary reactions occurring in the full reaction scheme are : CO + 1/2 02, NO + CO and C3H 8 + 10 NO. The results, and conditions, corresponding to this series of experiments are given in Tables 2-4. It can be seen that for the CO/O2 and NO/HC reactions, the 50% conversion temperature does indeed decrease with catalyst mass. /xm interesting phenomenon is noted for the NO/CO reaction (Table 3); when the catalyst is fresh, the 50% conversion temperature decreases with catalyst mass, in the manner expected. Once activated, however, we observe that the 50% conversion temperature is constant between 100 and 300 mg. Thus, as noted by several workers [17-21], we suggest that there is some degree of surface reconstruction occurring during the reaction. This very hnportant concept could explain the lack of correlation between activity and mass when operating under the full gas mixture. However, further investigations are necessary, and are discussed in subsequent sections. Table 2. Temperatures (~ for 50% CO conversion during the C 0 / 0 2 reaction over Pt-Rh/Al203 a 100 mg 200 mg 300 mg

CO 221 213 200 a Oscillating about SN=I , +/- 0.25 unit; frequency 0.05 Hz; Mean concentrations (ppm)- CO, 11000; 02, 5300.

154

Table 3. Temperatures (~ for 50% NO and CO a conversions during the NO~CO reaction for afresh, and used sample of Pt-Rh/Al203 b 100 mg 200 mg 300 mg Fresh Catalyst

297

284

264

Used Catalyst 289 291 293 a Conversion of NO and CO was simultmaeous. b Oscillating about SN-1, +/- 0.25 units; frequency 0.05 Hz; Mean concentrations (ppm) - NO, 3600; CO, 3600.

Table 4. Temperatures (~ for 50% NO and HC conversions during the NO/HC reaction over Pt-Rh/Al203a .... 100 mg 200 mg 300 mg .... NO

355

348

339

HC 380 352 356 a Oscillating SN=0.33, +/- 0.06 traits; frequency 0.05 Hz; Mean concentrations (ppm) - NO, 2600; HC, 900

(iiO The effect of frequency and oxidismg/reducmg strength on the catalytic activity Varying the frequency of switching between reaction media of different oxidising/reducing strengths provides important information on how the activity of the system responds to excursions into rich and lean reaction enviroltments [5,6]. Table 5 shows the results obtained by operating the reaction under the full gas mixture under deeply reducing (SN=0.45), stoichiometric (SN=I.00) and deeply oxidising (SN=1.45) media using different cycling frequencies, and also under steady-state conditions. From the results presented in this Table it can be clearly seen that, under cycling conditions, CO and HC oxidation reactions under deeply oxidising conditions are less favoured than under stoichiometric conditions, indicating that excess 02 inhibits these reactions. In order to investigate this phenomenon we compare the 50% conversion temperatures at 0.05 Hz, 1 Hz and under steady-state conditions (Table 5). It can be seen that the oxygen inhibition effect is only observed when we operate under cycling conditions (even at frequencies as high as 1 Hz), implying that the effect associated with oxygen inhibition occurs very rapidly. We suggest that this effect could have two origins: a) A transient form of adsorbed oxygen which desorbs slowly from the surface of the catalyst during rich excursions,

155 b) Excess oxygen is consumed by forming inactive surface oxides of the noble metal(s). This latter explmmtion would support the earlier suggestion that there is some degree of surface reconstruction occurring during the reaction. It has to be noted that the increase of the steady-state light-off temperature of the hydrocarbon from 289 to 311~ when going from stoichiometric to lean conditions does not implie the same phenomenom, indeed we think that the hydrocarbon reaction involves two different pathways, i.e. oxydation by both 02 and NO.

Table 5. Temperatures (~ for 50% conversion of CO, NO and HC over Pt-Rh operatmg under different frequencies and activities a Frequency Conversion of SN=0.45 b SN=I.00 c SN=1.45 d

(Hz) 0.05

CO

250

233

245

0.05

NO

270

299

0.05

HC

550

283

328

1

CO

268

228

239

1

NO

277

310

1

HC

568

300

345

Steady-state

CO

251

229

217

Ste ady- state

NO

260

297

Steady-state

HC

29%e

289

311

a Oscillating about chosen point +/- 0.1 unit;

b Concentrations (ppm) - CO, 12400; NO, 2600; 02, 3700; HC, 980. e Concentrations (ppm) - CO, 5000; NO, 2150; 02, 6500; HC, 980. d Concentrations (ppm) - CO, 3600; NO, 1900; O2, 9400; HC, 1000. e Maximum conversion obtained. 3.2. The activity of single metal catalysts as a function of mass

(i) 1% Pt/A1203 The variation in activity with catalyst mass, for the full gas mixture operating under cycling conditions, over a single metal Pt catalyst was measured to try to assess the roles of the different metals in the bimetallic catalyst. The results obtained from these experiments are presented in Table 6. It is clear that

156 the temperatures for 50% conversion of CO, NO and HC decrease with increased catalyst mass. In the absence of diffusion limitations this trend is expected, nevertheless, it was not observed for the parallel experiments with the bimetallic catalyst (Table 1). This result again provides evidence that surface rearrangement occurs on the Pt-Rh catalyst. An interesting observation cma be made by comparison of Tables 1 and 6 (for similar catalyst masses). It can be seen that the monometallic Pt catalyst is more active than the bimetallic system when operating about stoichiometry, this result suggests that the addition of Rh appears to deactivate the catalyst. The reason for the addition of Rh becomes apparent when studying the reaction under reducing conditions, and is discussed more filly in the following section. Table 6. Temperatures (~ f o r 50% conversion o f CO, NO and HC over 1% P t/A l 20 3a .. 100 mg 200 mg 300 mg

CO

216

208

198

NO

283

279

276

HC 277 271 266 a Oscillating about SN=I, +/- 0.1 unit; frequency 0.05 Hz; Mean concentrations (ppm): CO, 5600; NO, 2050; 02, 6000; HC, 900. (i 0 1% Rh/Al20 3 From Table 7, we observe that the 50% conversion temperatures for CO, NO and HC decrease with increased catalyst mass as observed in the case of the monometallic Pt catalyst. This Table shows that, under stoichiometric conditions, Rh is considerably less active than the Pt and Pt-Rh catalysts. In the case of NO, the difference is somewhat exagerated since our Tables show temperatures corresponding to the complete reduction of NO to N2. However, over the Rh catalyst, large alnotmts of N20 formed from the partial reduction of NO are observed, an observation which has been noted previously over the Pt-Rh catalyst. Figure 2 shows the NO conversion profiles for Pt-Rh, Pt and Rh catalysts operating under stoichiometric conditions. It is to be noted that, when operating under stoichiometric conditions, the Rh catalyst is considerably less active than both the Pt and Pt-Rh catalysts. The reason for the inclusion of Rh in the bimetallic system becomes clear when we study the activity under deeply reducing, and oxidising conditions [24]. Our results show that under deeply oxidising conditions Rh fonns an inactive surface

157

oxide (thought to be Rh203) , whereas under deeply reducing media Rh greatly enhances the activity for CO, NO and HC conversion. Table 7. Temperatures (~ for 50% conversion of CO, NO and HC over 1% Rh/AI203 a 100 mg 200 mg 300 mg

CO

280

266

192

NO

445

399

386

HC 428 396 384 a Oscillating about SN=I, +/- 0.1 unit; frequency 0.05 Hz; Mean concentrations (ppm)" CO, 5600; NO, 2050; O2, 6000; HC, 900. Thus, we suggest that when the bimetallic catalyst operates under cycling conditions, lean excursions lead to the formation of an inactive surface oxide, which we suggest as being Rh203. During rich, and stoichiometric, excursions the metals exist in a filly, or partially, reduced state, this oxide does not form and the Pt-Rh alloy remains. It is this change in surface structure which is thought to be responsible for the phenomena noted in this publication., Results in Table 5 seem to show that the surface changes occur within at most 10 seconds because of the range of frequencies studied, but the time taken for these processes to occur is currently under investigation In order to further investigate these surface rearrangement processes, the reaction of CO and 02 has been studied using the 'step-change' procedure. 103 80 Pt-Rh

60

~1 ~ sRh

40

--

-

-

Pt

20

j 50

l 100

150

I ~"1 I 200

250 300

350

400

450

500

Temperature/~

Figure 2 9Conversion of NO vs. temperature for the Pt-Rh, Rh and Pt catalysts

158

3.3. Step change experiments on Pt-Rh/AI203 0 Fresh catalyst, oxidation step (C0-02-C0) During the first transition (CO-O2), a rapid desorption of CO2 is observed as soon as the gas is switched to 02. The CO2 is formed by the surface reaction of preadsorbed CO and 02 via the well-known Langmuir-Hinshelwood mechanism. The exact amotmt of CO2 liberated, and the peak baseline width, are given in Table 8. After t2, the catalyst is subjected to the second transition (02CO), and a second CO2 peak is observed. We suggest that during t2, all the preabsorbed CO reacts, and is replaced on the surface by 0 2. After t2, CO2 is formed by the surface reaction of preadsorbed 02 with CO.

ii) Fresh catalyst, reduction step (02-CO-Oz) Once again, two CO 2 peaks are observed, however, their characteristics are somewhat different to those observed during the oxidation test (Table 8). During the O2-CO step we observe an initial, rapid evolution of CO2, thought to be due to the rapid surface reaction of coadsorbed O2 and CO. This peak however, takes nearly 48 minutes to return to the baseline (compared to 6.9 minutes for the O2-CO step in the oxidation test). We suggest that the reason for this is that, during the oxygen pretreatment, the catalyst surface becomes oxidised; switching to CO causes the oxide to be reduced which is shown to be a long process.

iiO C0/02 reaction over a reacted catalyst In order to further study the processes occm"ring on the catalyst surface after exposure to the fill gas mixture, a sample of the catalyst was heated to 450~ under the conditions given in the footnote to Table 1. After reaching 450~ the catalyst was cooled to 300~ under N 2 and the step-change experiments were carried out as previously described. The results are reported in Table 8. For the oxidation test, both the amounts of CO 2 formed, and the baseline widths, are different to those obtained for the flesh catalyst. This result suggests that exposure of the catalyst to the fidl reaction mixture causes a rearrangement of the surface structure. For the reduction test, we see that the C02 peak areas, and the corresponding baseline widths, for both the flesh and reacted catalysts are similar, showing that, as opposed to a reducing pretreatment, pretreating the catalyst in oxygen leads to a surface composition which is well defined, regardless of the state of the surface prior to the pretreatment.

159

Table 8. Peak areas, and baselme widths for the C0/02 reaction observed by the step-change procedure for the fresh' and 'reacted'catalysts

First Peak Area

C0-02CO a Fresh

02-C0O2 b Fresh

C0-02CO a Reacted

02-C0O2 b Reacted

1.1 x 104

1.0 x 105

2.4 x 104

1.0 x 105

2.3

47.9

14.8

41.3

3.3 x 104

1.8 x 104

4.9 x 104

1.9x 104

6.9

2.5

11.9

4.5

(ppm.s) First Peak Width (mins) Second Peak Area (ppm.s) Second Peak Width

(mins) a tl = 10 mins; tN = 15 mins; t2 = 15 mins. b tl = 10 mins; tN = 15 mins; t2 = 60 mins.

4. CONCLUSIONS

It has been shown in this publication that interesting surface phenomena occur on the surface of a Pt-Rh/A1203 catalyst when exposed to mixtures of CO, NO, 02 and C3H8. We have observed that, for the bimetallic catalyst, the 50% conversion temperatures do not increase with mass in the expected maimer, whereas the expected correlation is observed for the Pt/A1203 and Rh/A1203 single metal catalysts, implying effects associated with the bimetallic system. By varying the oxidising/reducing strengths of the reaction media, and also the frequency of cycling between the two media we have provided evidence for an hfllibiting effect of oxygen. By comparison with results obtained under steadystate conditions we have shown that this effect is a transient phenomenon associated with switching between different reaction compositions. Using step-change experiments on flesh and aged catalysts we have shown that exposure to reaction conditions does indeed cause a surface rearrangement to occur. When the catalyst is exposed to a reducing or stoichiometric reaction envirolunent, we observe an activity attributed to reduced surface metals, whereas under oxidising conditions, the catalytic activity is due entirely to Pt,

160

with Rh forming the inactive surface oxide Rh203, this phenomenon occurs regardless of the state of the surface prior to oxidation. ACKNOWLEDGEMENTS

Tlfis work was carried out within the 'Groupement de Recherche sur les Catalyseurs de Postcombustion'. Thanks are due to the Institut Frangais du Petrole for the grant for C.H.

REFERENCES

5 6 7 8 9 10 11 12 13 14 15 16 17

H.S. Gandhi, M. Shelef, Catalysis and Automotive Pollution Control, A. Crucq and A. Frel~let(F_,ditors),ElsevierSciencePublishers,Amsterdam, 1987,199. Proceedings from CAPoC1 and CAPoC2, Catalysis and Automotive Pollution Control, A. Cnlcq and A. Fremlet (Editors), Elsevier Science Publishers, Amsterdam, 1987 and 1991. B. Hans A.F. Diwell,C. HaUett,PlathltnnMetalsRev., 32(2), 1988,73. R.K. Herz, Catalysis and Automotive Pollution Control, A. Crucq and A. Fremlet (Editors), Elsevier Science Publishers, Amsterdam, 1987,427. J.C. Sd~er, R.M. Sinkevitd~,PJ. Nfitd~ell,hxt.Eng Clx~rL~ Res.~ . , 22,1983, 51. J.C. Schlatter,P.J. Mitchell,had.Faag.Chem.Prod. Res. Des. Dev., 19, 1980,288. T. Engel, G. Ertl, J. Chem. Phys., 69, 1978, 1267. B.E. Niewenhuys, Surf. Sci., 126, 1983, 307. T. Engel, G. Ertl, Adv. Catal., 28, 1979, 1. W.C. Hecker, A.T. Bell, J. Catal., 59, 1979, 223. SJ-~ Oll, G.B. Fisher,J.E. Carl~ter, D.W. Gcxxtman,J. Catal., 100,1986, 360. S.B. Schwartz, G.B. Fisher, L.D. Sclunidt, J. Phys. Chem., 92, 1988, 389. H.A.C.M. Hendrickx, A.M.E. Winkehnan, B.E. Niewenhuys, Appl. Surf. Sci., 27, 1987, 458. H. Abderrahim, D. Duprez, Catalysis and Automotive Pollution Control, A. Cnlcq mad A. Fremlet (Editors), Elsevier Science Publishers, Amsterdam, 1987, 359. J.A. Anderson, J. Catal., 142, 1993, 153. Se.H. Oh, C.C. Eickel, J. Catal., 128, 1991, 526. A.G. van den Bosch-Dreibergen, M.N.H. Kieboom, A. van Dretunel, R.M. Wolf, B.E. Niewenhuys, Catal. Lett., 2, 1989, 73.

161 18 19 20 21 22 23 24

A.G. van den Bosch-Dreibergen, M.N.H. Kieboom, A. van Dreumel, R.M. Wolf, F.C.M.J.M. van Delft, B.E. Niewenhuys, Catal. Lett., 2, 1989, 235. J.Siera, R. van Silfllout, F. Rutten, B.E. Niewenhuys, Catalysis and Automotive Pollution Control, A. Crucq and A. Frelmet (Editors), Elsevier Science Publishers, Amsterdam, 1991,395. F.C.M.J.M. van Delft, G.H. Vurens, M.C. Angevarre-Gruter, B.E. Niewenhuys, Catalysis and Automotive Pollution Control, A. Crucq and A. Frelmet (Editors), Elsevier Science Publishers, Amsterdaln, 1987, 229. W.B. Williarnson, H.S. Gandhi, P. Wynblatt, T.J. Truex, R.C. Ku, A. I. Chem. Eng. Symposium Series, 76(201), 1980, 212. H. Kobayashi, M. Kobayashi, Catal. Rev. Sci. Eng., 10, 1974, 138. M. Weibel, Ph.D. Thesis, Universit6 Louis Pasteur, Strasbourg, 1991. C. Howitt, V. Pitchon, Results to be published.



163

COMPARISON OF Pt/MnOx/SiO2 AND Pt/CoOx/SiO2 CATALYSTS FOR THE CO OXIDATION WITH 02 AND THE NO REDUCTION WITH CO

Y. J. Mergler, A. van Aalst, J. van Delft and B. E. Nieuwenhuys Gorlaeus Laboratories, P.O. Box 9502, 2300 RA Leiden, The Netherlands.

ABSTRACT

Pt/MnOx/SiO2 and Pt/CoOx/SiO2 catalysts are efficient catalysts for the reduction of NO with CO and the oxidation of CO with 02 at low temperature, with a much lower on-set temperature for the reactions compared with Pt/SiO2. An oxidative pretreatment lead to a shift to higher light-off temperatures for O2 and NO conversion. For a pure CoOx/SiO2 catalyst primarily N20 was formed following an oxidation step. Over Pt/CoOx/SiO2 CO is already oxidised at room temperature. Three possible models to account for the high activity of Pt/CoOx/SiO2 in the CO/O2 reaction are presented and discussed. The highest NO conversion was reached by using the Pt/MnOx/SiO: catalyst. It was found that N20 is an important intermediate compound in CO/NO reactions over the Pt/MnOx/SiO2 catalyst. The performance of Pt/CoOx/SiO2 in CO/NO reactions is only slightly better than Pt/SiO2.

1. INTRODUCTION The present three-way catalyst (TWC) consists of the precious metals Pt (or Pd) and Rh. [1, 2] Platinum is very active in converting CO and hydrocarbons (hc) into the harmless compotmds CO2 and 1-120. It i s , however, not an efficient catalyst for the reduction of NO to N2 since it produces NH3 wader net reducing conditions. Whether N2, N20 or NH3 is fonned as a product of NO reduction over Pt depends on the reaction conditions [3-5]. Rhoditnn is highly selective towards N2 formation [4-6]. At present, more than 80% of the total worldwide production of rhodium is used in TWCs. According to stricter legislations to reduce automotive pollution, this

164 percentage is expected to increase even fitaher. As a result, rhodium may become scarce and more expensive. Another important point is that most of the he and CO is emitted following the cold start of the engine [7]. This has led to an urgent need to develop catalysts with improved activity at lower temperatures. On early research connected with automobile exhaust treatment many research groups studied the CO oxidation by 02 and by NO over several supported metal oxides [8]. Shelef et al. [8] reported that the oxides of Co, Cu, Mn and Ni are the most active of the oxides examined in CO oxidation [9]. Supported metal oxides showed promising results in the treatment of automotive exhaust. A few years later, however, it was realised that supported noble metals performed better with respect to the conversion of CO, hc and NOx, and are less susceptible to poisoning by S or P [1,10]. Several studies were performed to explore the use of metal oxides in combination with supported Pt or Pd as a possible replacement for Rh. Regalbuto et al. and Gandhi et al. used WO3 and MoO3 respectively as an additive to Pt to improve their catalysts for CO/NO reactions I11, 12]. Muraki et al. and Halasz et al. added La203 and MoO3 respectively to their Pd supported catalysts [13, 14]. Continuing attempts are also being made to develop a TWC without noble metals. For example, Stegenga et al. [15] studied the combination of Cu-Cr supported on alumina catalyst. At the moment, a fair number of studies involve the use of zeolites, especially for NO~ reduction under lean conditions. This concept is not new, because Fe-Y-Zeolites were already investigated by Fu et al. [16]. Cu-Zeolites also exhibit reasonable characteristics towards NO~ reduction [17-19]. However, it is doubtful if a catalyst with no noble metals in it can replace the noble metal containing TWC for the present generation of gasoline-fuelled engines, in view of the strict legislations concerning automotive exhaust gases and catalyst lifetime. Recently, Pd-only catalysts have been introduced as commercial TWC [20]. These catalysts contain Pd as the only precious metal and, in addition, a number of non-classified oxides. This success demonstrates that the development of Rh-free TWC is no longer a utopia. However, it is unlikely that the Pd-only TWC can replace the Pt-Rh TWC on a large scale due primarily to the limited availability of Pd for TWC compared to Pt. In our studies, we have concentrated on the performance of Pt-only catalysts (Pt in combination with oxides) as a possible substitute for the PtRh TWC. In our laboratory it has already been established that Pt/MnOx and Pt/CoOx have promising catalytic properties for CO oxidation and NO reduction. In this paper we will compare the activity of Pt/MnOx/SiO2 and Pt/CoOx/SiO2 catalysts in CO oxidation by 02 and NO reduction by CO. Special attention will be given to the low temperature oxidation of CO.

165 2. EXPERIMENTAL

H2Pt(OH)6, dissolved in hot nitric acid, was used as a precursor and added to a silica suspension. A 5 w% Pt/SiO2 catalysts was made by urea decomposition [21]. After drying, this catalyst was reduced for 3 hours in flowing 1-12at 400~ Part of this reduced catalyst was impregnated with a cobalt nitrate solution. Another part with a manganese nitrate solution. The catalysts contained, after calcination in air at 400~ respectively 3 w% of Co304 (atomic ratio Pt:Co = 1:1.5) and 25 w% MnO2 (atomic ratio Pt:Mn = 1:15). A 3 w% CthOdSiO2 catalyst was made for comparison. In addition, a 50 w% CoOx/SiO2 was prepared for experiments using FTIR. These catalysts will be referred to as Pt/CoOJSiO2, PffMnOJSiO2 and CoOJSiO2 respectively. The catalysts were reduced in flowing 1-12, or oxidised in air, at 400~ for 3 hours, prior to the activity measurements. The measurements were performed in an atmospheric flow apparatus. The gases used were 4 vol% NO/He, 4 vol% CO/He and 4 vol% OJI-Ie (Hoekloos). The flow rate could be adjusted with mass flow controllers to a maximum of 40 ml/min. The CO/O~ and CO/NO ratios were varied from oxidising to reducing. Product and reactant analysis occurred by means of a mass spectrometer. The conversion of O2 or NO was plotted against the temperature at reducing or stoichiometric gas mixtures, while the conversion of CO was used at oxidising gas mixtures. The temperature was raised with 3~ to 400~ X-Ray diffraction, CO chemisorption and Fourier transform infrared spectroscopy were used for characterisation. Self-supporting disks were used for the IR measurements. Before pressing the catalyst into disks, the catalyst was first reduced in flowing H~ for 3 hours at 400~ The disks were placed in an IR cell, that could be evacuated to 10-5 mbar. The IR cell was placed in a sample compartment of a Fourier infrared spectrometer. (Galaxy 2020 from Mattson) This compartment, however, was not purged with an inert gas. As a result, no information about the possible formation of products like CO2 could be extracted. Thirty-two scans were taken with a resolution of 4 crn-~ for one spectrum. The catalysts were all reduced or oxidised in-situ, with 100 mbar H~ or O2, followed by an evacuation at 105 mbar for 30 min. Background spectra were taken at several temperatures at 105 mbar. Sample spectra were taken at several temperatures after the addition of 5 mbar CO or NO or a mixture of 10 mbar CO and NO.

166 3. RESULTS AND DISCUSSION

3.1. Characterisation

Table 1 shows the characteristics of the catalysts as measured by CO chemisorption and X-Ray Dit~aetion.

Table 1. Characteristics of the catalysts Disp. (%)

XRD (red)

XRD (ox)

Catalyst

mole CO/g cat.

Pt/SiO,

4.7 10"5

18

Pt, 16oA

PffMnO~/SiO,

1.9 105

10

Pt, 170A MnO, 150 A

Pt, 200 A MnO2, 190 ,,~

Pt/CoOJSi02

2.6 10"5

Pt, 55 A

Pt, 70 A

It was assumed that one CO molecule adsorbs per surface Pt atom. The dispersion of Pt/CoOx/SiO2 was not calculated because CoO~ also adsorbed CO. This can also be seen in the following FTIR spectra. By using X-ray diffraction, only the characteristic peaks ofPt ~ were found, regardless the pretreatment. Figure 1 shows the absorption bands when 5 mbar CO and 5 mbar NO were coadsorbed on the Pt/SiO2 catalyst. Only one band appeared, at 2070 cm ~, which can be ascribed to linearly bonded CO on Pt ~ [22]. There were no bands indicating NO adsorption. At higher temperatures no isocyanate complex bound to Pt was detected. (not shown). Figure 1 also shows the adsorption of 5 mbar CO on 50 w% CoOJSiO2 after a reductive pretreatment. (FTIR experiments of 3 w% CoOx/SiO2 revealed hardly any bands of CO and NO adsorption). A small band at 2178 cm q was fotmd, which disappeared after heating above 100~ This indicates that CO is adsorbed to an ionic form of cobalt. Busca et al. [23] identified a band at 2180 crn~ when they adsorbed 100 mbar CO on pure, outgassed cobalt oxide. They ascribed this band to CO bonded on unsaturated Co 3§ions. We assign the band at 2178 crn-~ to CO bonded to co-ordinative Co 3+. The adsorption of 5 mbar NO on CoOx/SiO2 is also shown in figure 1. Two characteristic bands for NO bound to cobalt oxide were visible at 1858 and 1784 c m 1. They were assigned to linear and bent NO, respectively [24, 25]. Co-adsorption of CO and NO led only to bands of linear and bent NO on cobalt oxide. No indications of the formation of isoeyanate groups were found.

0

b' n C

e

I

Vave number (i/cm)

Figure 1.

Figure 2.

2200

2000 1800 Nave number (i/cmI

Figure 3.

Figure 1. FTIR spectra: a) Co-adsorption of 5 mbar CO with 5 mbar NO on PVSiO, at 100°C, b) Adsorption of 5 mbar CO on 50 w% CoOx/Si02at 25OC, c) Adsorption of 5 mbar NO on CoOx/Si02at 100°C. Figure 2. FTIR spectra: a) 5 mbar CO introduced to Pt/CoOx/Si02at room temperature, b) Introduction of 5 mbar NO at 100°C, c) 150°C, d) 200°C, e) 250°C, f) 300°C, g) 350°C. Figure 3. FTIR spectra: a) Co-adsorption of 5 mbar CO and 5 mbar NO on MnOx/SiO, at 250°C, b) Co-adsorption of 5 mbar CO and 5 mbar NO on Pt/MnOx/Si02 at 250°C, c) 350°C, t = 14 min, d) 350°C, t = 46 min.

1600

I

168 Figure 2 shows the adsorption of CO and NO on Pt/CoOJSiO2 at different temperatures. When CO was introduced at room temperature a band at 2066 cm 1 appeared, ascribed to linear CO bound to Pt~ This band at 2066 cm~ is broader at the base, but no distinct shoulder or band around 2020 cm ~ could be distinguished. This was different for a Pt/CoOJSiO2 catalyst containing 50 w% CoO~ where, after a reductive pretreatment at 400~ also a band at 2023 cm -1 was found. This band arose from linearly bonded CO on Co ~ (These results are not shown here). Atter the introduction of NO at 100 ~ bands of linear and bent NO were found at 1867 and 1792 cm~, respectively. The band at 2060 cm "~ is ascribed to linearly bonded CO on Pt ~ A new band at 2201 cmq showed up at this temperature, which increased in intensity when the temperature was raised to 250~ This band at 2200 c n ] "1 w a s neither found upon the co-adsorption of CO and O~ on the reduced Pt/CoOJSiO2 catalyst, nor after the addition of CO to an oxidised Pt/CoOJSiO~ catalyst. In conclusion, the band at 2200 cm~ could not be ascribed to CO adsorbed on Co s+. Yao and Shelef [26] found a small band at 2190 cm ~ on pure cobalt oxide when CO and NO were co-adsorbed, which they ascribed to -NCO on cobalt oxide. We therefore believe that the band at 2200 cm ~ originates from isocyanate on cobalt oxide. When the temperature was increased from 200 to 250~ the bands of linear and bent NO on cobalt oxide almost disappeared, while the oNCO band increased. More NO is dissociated at higher temperatures, leading to more Na and more -NCO. The formation of-NCO can proceed on Pt [22]. Migration of the -NCO group to the carrier is possible. This process is rapid or slow, depending on the carrier. Solymosi et al. and Anderson et al. found that the migration of oNCO to SiO2 is a very slow process. On alumina, however, this process is so rapid that no isocyanate on Pt could be distinguished [27, 28]. No oNCO bands were found on Pt/SiO2 upon the co-adsorption of CO and NO, up to 300~ This can mean either that 300~ is too low to start the dissociation of NO or that the oNCO reacts f l u t e r with NO to N2 and CO~ [29]. The mechanism by which the -NCO formation takes place is not yet clear. Is -NCO formed on Pt with a concomitant migration to cobalt oxide? Alternatively, does CO~ on Pt metal spill-over to N~ on cobalt oxide? Or does the reaction between N~ and CO~ take place only on cobalt oxide? The latter model may explain why the -NCO formation starts at temperatures as low as 100~ while at 100~ the NO dissociation on Pt~ is unlikely due to the inhibition of Pt ~ sites by CO. However, in our opinion, the third model is also rather tmlikely since we did not find any -NCO upon the co-adsorption of CO and NO over our CoOx/SiO2 catalyst. It must be noted, however, that Yao and Shelef did detect -NCO on their pure cobalt oxide [26]. Model two is the most likely of all the models presented above. This means that an increase in the intensity of the 2200 cm-' band will be accompanied by

169 a decrease in the intensity of the Pt-CO band. Figure 2 shows that this is the case between 200 and 250 ~ Isocyanate groups were formed above 250~ when CO and NO were coadsorbed on MnOx/SiO2 (figure 3). When NO and CO were added to PffMnOdSiO2, the formation o f - N C O started at around 150~ The isocyanate band grew in intensity when the temperature was raised to 350~ The bands of Pt-CO and -NCO were not stable at this temperature, because they disappeared after 45 minutes. We detected no bands of linear or bent NO, or CO-bands on manganese oxide.

3.2. CO oxidation by 02 Table 2 shows the results obtained for the Pt/SiOz, Pt/CoOx/SiO~ and PffMnOdSiO2 catalysts after a reductive pretreatment and after an oxidative pretreatment in CO oxidation by Oz. Table 2. Temperature (~ of 50 % 02 (CO)* conversion at several C0/02 ratios after a reductive or an oxidative ~retreatment. Ratio

C0"02

Catalyst

Pretreatment

3"1

2"1

1"1

Pt/Si02

Reduction

204

210

175

Oxidation

210

210

187

Reduction

29

26

15

Oxidation

103

103

101

Reduction

125

114

94

Oxidation

162

173

150

Pt/CoOdSi02

WMnOx/Si02

* Conversion of O2 in case of reducing or stoichiometric gas mixtures and conversion of CO in case of oxidising gas mixtures. The performance of Pt/CoOx/SiO: is superior to Pt/MnOx/SiO2 and Pt/SiO2. Over Pt/CoOx/SiO: CO is even oxidised at room temperature after a reductive pretreatment. Below 100~ all the CO (or 02) was converted. The temperature of 50% CO (or O2) conversion increased by 75~ to a higher temperature after an oxidative pretreatment. Hence, the performance of Pt/CoOdSiOz is still much better than those of Pt/MnOx/SiO2 and PffSiO2. PffMnOx/SiO2 showed an intermediate behaviour compared to the performance of Pt/SiO2 and Pt/CoOx/SiO2. An oxidative pretreatment increased the temperature of 50% conversion by only 25 - 50~

170

Oxidation or reduction as pretreatment had no significant effect on the CO oxidation by 02 over Pt/SiO,. Upon comparing the activity of the Pt/SiO~ catalyst for the various CO/O2 ratios, it was found that CO inhibition occurred. This effect was less marked for the Pt/MnOJSiO2 and Pt/CoO,/SiO~ catalysts. The question arises why Pt/CoOJSiO2 shows such a good CO oxidation behaviour, especially at~er a reductive pretreatment. The Pt/CoOJSiO~ catalyst is more active ~ e r a reduction than after an oxidation. At~er an oxidative pretreamaent Pt ~ was detected using X-ray diffraction with an average particle size of 70 A (table 1). With higher weight percentages cobalt oxide, CoPt, CoPt3 and Co o peaks could be detected following reduction at 400~ (Not shown here). It is possible to form alloy particles of Pt and cobalt under our reductive pretreatment conditions, but in the case of the Pt/CoOJSiO, with 3 w% Co304 no alloy particles could be identified with XRD. When they studied the CO oxidation reaction, Meunier et al. found that Co 2+ ions in Pt/CoOJAI,O3 catalysts dissociate oxygen more easily than Co 3+ [30]. Partially reduced CoO~ is apparently necessary for O~ dissociation. Pande and Bell [31] found a high activity of Rh/TiO2 for the NO reduction by H2. The authors attributed the promoting effect of TiO~ to the presence of catalytically active TiO~ centres on the support as well as on the surface of the supported Rh crystaUites. Low-temperature CO oxidation by Oz proceeds between 25 and 100~ over a Au/MnO~ catalyst, as was shown by Gardner et al. [32]. The Au/MnO~ catalyst performed even better than the commercially available Pt/SnO~ in CO oxidation reactions [32]. No mechanism was presented to account for the observed activities for these catalysts. It has been suggested by Nieuwenhuys [33] that MnO~ serves as dissociation centres for O2. Oxygen atoms can spill-over from MnO~ to Au, in the presence of the reactant gases. Gold itself is not active in O-O bond scission. However, O adatoms are stable on Au at room temperature. In the presence of CO the O adatoms can easily react with CO due to the low Au-O bond strength [33].

C02

C02 0

/

I

rf

o

0

I

/

l'I

C l'I

/"s'•

Pt

I

Pt

/

0 C

0

i=t

l'I

I

/

C

I

/

/

l'I

rf

p-~

/ sio2

Pt

I

/

Pt

/

Figure 4. Second and third model for the reaction of CO with 02 over Pt/CoO/SiO~. (See text).

171 CoOx may affect the adsorption of CO or O2 on Pt. Since at low temperatures the reaction rate on Pt is determined by the slow adsorption of oxygen due to CO inhibition, it is most likely that CoO~ serves as O-supplier for the reaction. No influence of cobalt oxide on the CO adsorption on Pt was detected by IR measurements. If we assume that Pt-Co alloy formation does not play an important role in the CO/O2 reaction over Pt/CoOJSiO2, several models may account for the observed effects. According to our first model, cobalt cations enhance the adsorption of 02 on Pt by an increased electron back-donation into the anti-bonding orbitals of O2, which facilitates 02 dissociation. The increased back donation may be induced by the electrical field of the cobalt cations. The second model is shown schematically in figure 4. CO is adsorbed on Pt. 02 dissociates on CoOx and the dissociation may be assisted by the presence of O-vacancies present on cobalt oxide. CO~ on Pt will react with O~ on cobalt. This reaction will then take place at the interface between Pt and CoOx. It is also possible that Oa migrates from the CoO~ to Pt, in which case the reactien proceeds on the Pt surface (third model). The authors are in favour of the last two models since Pt itself is already able to dissociate O2 around 100 K if flee Pt sites are available (no CO inhibition) [33].

3.3. NO reduction by CO The two possible reaction pathways are: 2CO + CO +

2NO---> N2 + 2NO--->N20 +

2CO~ CO2

(1) (2)

N20 is believed to be an important intermediate product in the CO/NO reaction [9, 34]. At higher temperatures N20 may react fiuther according to (3) or may decompose [34]. The following reaction can proceed: CO +

N20 ---> N2

+

CO2

(3)

Since the masses of CO/N2 and CO~q20 are equal and the fact that our mass spectrometer is not sensitive enough to monitor masses 14 of N, 16 of O accurately, only the differences in activity of the Pt/SiO2, 3 w% CosO4/SiO2, Pt/CoOJSiO2 and Pt/MnOx/SiO2 catalysts could be measured. Figures 5a to 5c and 6a to 6c show the results of the catalysts in the NO reduction by CO atter a reductive or an oxidative pretreatment, respectively. The sequence of the activity of the catalysts in the CO/NO reaction is different from that of the CO/O2 reaction. Pt/MnOx/SiO2 is more active than Pt/CoOx/SiO2. Figure 6a also shows the NO conversion over CoOx/SiO2 after an oxidative

172 pretreatment. It is noteworthy that the maximum in NO conversion was around 3000(2 for PffMnOJSiO2 and for CoOflSiO2 (fig 6a). Reaction 2 is favoured at lower temperatures, because then the NO coverage is high and the N coverage low, resulting in a high rate of N20 formation and a low rate of N2 formation [35-37]. Figure 5a shows the presence of a maximum in the NO conversion around 300~ for the CoO~ catalyst. A similar maximum in NO conversion was also found in NO/H2 reactions over Pt/CoOx/SiO2 catalysts [38]. This maximum corresponds to the maximum in N20 formation. Thus it seems that the maximum in conversion observed for the CO/NO reaction around 300~ is also caused by N20 formation. N20 decomposes around 350~ [9, 38], leading to a maximum in the NO conversion curve. This suggests that the main reaction over the oxidised cobalt oxide catalyst is reaction 2 at lower temperatures. The assumption that reaction 2 is important at low temperatures over oxide catalysts may also explain the excellent activity of Pt/MnOx/SiO2 at lower temperatures. At higher temperatures reaction 3 proceeds, but primarily over the Pt species of the Pt/MnOJSiO2 catalyst The NO conversion at lower temperatures of PffMnOJSiO~ can be explained by the preferential formation of N20, as stated above. The activity of Pt/CoO,,/SiO2 in CO/NO reactions was only slightly better than Pt/SiO~. Since cobalt oxide is able to dissociate NO (fig 6a) at around 200~ it is difficult to understand why no N20 formation starts at around 200~ on Pt/CoOx/SiO2. In our opinion this is due to the formation of-NCO on cobalt oxide, which blocks the active sites for NO adsorption and dissociation. NO starts to dissociate on cobalt oxide but a rapid formation and build-up of-NCO retards the dissociation on cobalt oxide. Platinum is then the only species available for NO dissociation, leading to temperatures of 50 % NO conversion that are almost equal to the temperatures of 50 % NO conversion over Pt/SiO2. Excess CO results in the formation of more -NCO [29]. With excess NO the reaction of isocyanate with NO is expected, leading to N2 and CO2 production [39]. Isocyanate is regarded as a spectator species [29]. The higher activity of the Pt/CoOx/SiO2 catalyst with excess NO, can be explained by a decrease in the blockade by -NCO of the active CoO~ species. Preadsorbed oxygen stabilises the NCO band [40]. This may explain the small differences in the temperatures of 50 % NO conversion after a reductive or an oxidative pretreatment; after an oxidation the NCO is stabilised and affects the activity by blocking cobalt oxide, resulting in higher temperatures of 50% NO conversion.

0 0

100

m

Temperature ( C)

Figure 5a.

0

0

3ca

400

0

100

200

300

Temperature ( C)

Figure 5b.

400

0

loo

200

300

Temperature ( C)

Figure 5c.

Figure 5. NO conversion versus temperature in the NO reduction by CO over PtISiO,, Pt/CoO,/SiO, and Pt/MoOc/SiO, after a reductive pretreatment with a C0:NO ratio of a) 1:1, b) 3:1, and c) 1:2.5 (CO convelkion).

400

0

0

0

0

1W

200

300

Temperature ( C)

Figure 6a.

400

0

1W

200

300

Temperature ( C)

Figure 6b.

4W

0

1W

200

300

Temprature ( C)

Figure 6c.

Figure 6. NO conversion versus temperature in the NO reduction by CO over PtISiO,, PtlCo0,/Si02 and Pt/MnOx/Si02 after an oxidative pretreatment with a C0:NO ratio of a) 1:1, b) 3 1 , and c) 1:2.5 (CO conversion).

400

175 3.4. Comparison of PffMnO~/SiOz and Pt/CoO~/SiOz in CO/O2 and CO/NO

reactions The results presented above show that a partially reduced catalyst performed better in CO oxidation and NO reduction. Partially reduced centres are apparently necessary to enhance low temperature 02 and NO dissociation. In the case of Rh single crystal surfaces, Wolf et al. [35] found direct evidence that vacancies are required for the dissociation of NO molecules. A high coverage of molecularly adsorbed NO inhibits the reaction rate at low temperatures because of the limited availability of vacancies on the surface of the noble metal. Partially reduced metal oxides may provide for the dissociation centres for NO. This was also shown by Tomishige et al., who studied the promoting effect of Sn on NO dissociation and NO reduction with H2 over Rh-Sn/SiO2 catalysts [41]. They found that NO even dissociated at room temperature on a reduced Rh-Sn/SiO~ catalyst and that the rapid dissociation stopped when one-third of surface Sn atoms was oxidised by NO. An oxidative pretreatment increases the temperatures of 50 % conversion, but overall the activity is still better than that of Pt/SiO2. Cobalt and manganese oxides can be reduced very easily, especially when Pt~ is present [41 ]. CoOx is itself active in CO/NO, especially after an oxidative pretreatment. Pt/CoOx/SiO2 is very good in low-temperature CO oxidation, while Pt/MnOx/SiO2 shows an intermediate behaviour between Pt/CoOx/SiO~ and Pt/SiO2. In CO/NO reactions, however, PffMnOJSiO2 is better than Pt/CoOx/SiO2 when the NO conversion activity is compared, but the selectivity is to N20 at lower temperatures. The isocyanate bands on Pt/MnOJSiO2 and Pt/CoOx/SiO2 are not stable above 350~ No bands of adsorbed CO or NO were found on manganese oxide, while linear and bent NO were clearly visible on cobalt oxide. The decoration with -NCO, resulting in an inhibition of the CO/NO reaction at lower temperatures, took place over Pt/CoOx/SiO2.

4. CONCLUSIONS

Pt/MnOx/SiO2 and Pt/CoOx/SiO2 catalysts have a lower onset temperature for the reaction of CO with 02 or NO. An oxidative pretreatment led to a shift to higher temperatures for Oz and NO conversion. In the case of a pure CoOJSiO2 catalyst, primarily N20 was formed following an oxidation step. When a Pt/CoOx/SiO2 catalyst was used, CO was even oxidised at room temperature. A number of possible models have been discussed to explain the high activity of Pt/CoOJSiO2 in the CO/Oz reaction. In our opinion the models for CO

176

oxidation by 02 in which O-vacancies on the CoOx play an important role as dissociation centres for 02 are the most acceptable models. Pt/CoOJSiO2 is the most active catalyst in CO oxidation at low temperature, while PffMnOJSiO2 had the highest NO conversion in CO/NO reactions. However, N20 is an important primary reaction product, using the Pt/MnO~/SiO2 catalyst. The performance of Pt/CoOx/SiO2 in CO/NO reactions was rather disappointing. Its activity was only slightly better than Pt/SiO2. This may be due to the formation of isocyanate groups on the cobalt surface, leading to blocking of the active sites needed for dissociation of NO. ACKNOWLEDGEMENT

We would like to thank the Johnson Matthey Technology Centre (Reading, U.K.) for the loan of the Pt salt. This research was financially supported by SON/STW, project number 349 1878. REFERENCES

1 2 3 4 5 6 7 8 9 10 11 12 13

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177 14 I. Halasz, A. Brenner, and M. Shelef, Catal. Lett., 16 (1992) 311 15 S. Stegenga, Thesis, Ulfiversity of Amsterdaln, Sept. 1991 16 C. M. Fu, M. Deeba, W. K. Hall, hid. Eng. Chem. Prod. Res. Develop., 19 (1980) 299 17. M. Shelef, Catal. Lett., 15 (1992) 305 18 Y. Li, and W. K. Hall, J. Catal., 129 (1991) 202 19 M. Iwamoto, H. Yalfiro, K. Tanda, N. Miztmo, Y. Mine, and S. Kagawa, J. Phys. Chem., 95 (1991) 3727 20 J. C. Summers, and Williamson, W. B., in: Environmental Catal. ACS Symposium Series 552, Armor, J. N., (eds.), 1994, 94 21 J. W. Geus, Dutsch Patent Application 6, 705 (1967) 259 22 G. M. Alikina, A. A. Davydov, and I. S. Sazonova, Kin. i Kataliz., 27 (1986) 875 23 G. Busca, R. Guidetti, and V. Lorel~elli, J. Chem. Soc. Faraday Trans., 86 (1990) 989 24 H. Niiyama, and E. Eclfigoya, J. Catal., 38 (1975) 238 25 T. Islfihara, K. Eguclfi, and H. Arai, Chem. Lett., (1986) 1695 26 H. C. Yao, and M. Shelef, J. Phys. Chem., 78 (1974) 2490 27 F. Solymosi, L. V01gyesi, and J. SS,rkS,ny, J. Catal., 54 (1978) 336 28 J. A. Anderson, and C. H. Rochester, J. Chem. Soc. Faraday Trans., 86 (1990) 3809 29 W. C. Hecker, and A. T. Bell, J. Catal., 85 (1984) 389 30 G. Metmier, F. Garb1, J. Schmitt, G. Maire, and R. Roche, Stud. Surf. Sci. and Catal., 30 (1987) 243 31 a) N. K. Pande, and A. T. Bell, J. Catal. 98 (1986) 7; b) Appl. Catal. 20 (1986) 109 32 S. D. Garchler, G. B. Hofltuld, B. T. Upchurch, D. R. Scl~yer, E. J. Kielin, and J. Scl~3,er, J. Catal. 129 (1991) 114 33 B. E. Nieuwenhuys, h~ "Elementary Reaction Steps ha Heter. Catal.", R. W. Joyner and R. A. van Santen (eds), Kluwer, (1993) 155 34 B. K. Cho, B. H. Shanks, and J. E. Bailey, J. Catal. 115 (1989) 486 35 R. M. Wolf, J. W. Bakker, and B. E. Nieuwenhuys, Stu-f. Sci. 246 (1991) 135 36 H. Hirano, T. Yamada, K. I. Tanaka, J. Siera, and B. E. Nieuwenhuys, in "New Frontiers hi Catalysis", Guczi, L. et al. eds., 345 (1993) (Proc. 10th h~t. Cong. Catal., 1992, Budapest) 37 H. Hirano, T. Yamada, K. I. Tanaka, J. Siera, and B. E. Nieuwenhuys, Surf. Sci. 97 (1992) 262 38 Y. J. Mergler, A. van Aalst, and B. E. Nieuwenhuys, accepted for publication fir Proceedhlgs of the ACS Sympositun on NO~ reduction, San Diego, 1994 39 H. Niiyama, M. Tanaka, H. Iida, and E. Eclfiogoya, Bull. Chem. Soc. Jpn., 49 (1976) 2047 40 F. Solymosi, and J. Rasko, Appl. Catal., 10 (1984) 19 41 K. Tomishige, K. Asakura, and Y. Iwasawa, J. Chem. Sot., Chem. Comlntm., (1993) 184



179

REDUCTION BEHAVIOR OF Rh-Sn/SiO2 BIMETALLIC CATALYSTS AND ITS CO OXIDATION ACTIVITY Satoru Nishiyama, Ikuo Yamamoto, Masahiro Akemoto, Shigeru Tsuruya, and Mitsuo Masai Department of Chemical Science and Engineermg, Faculty of Engineermg, Kobe University, Rokkodai, Nada, Kobe 657, Japan ABSTRACT

Reduction behavior of Rh-Sn on SiO2 was studied by temperature programmed reduction methods. During the reduction of Rh-Sn/SiO2 preoxidized, Rh oxide was reducible in the range of 370-440 K first, then the reduction of Sn oxide proceeded at a higher temperature up to 470 K. X-ray diffraction powder patterns indicates that the higher temperature than 673 K was required in order to obtain well-mixed Rh-Sn bimetallic system. The catalyst reduced at 673 and 773 K indicated the high activity for CO oxidation reaction at low reaction temperatures. These results indicate the reduction behavior in the following; Rh oxide was reduced first and metallic Rh was formed, then Sn oxide was reduced by the spillover hydrogen which was formed on the metallic Rh particles. Finally, bimetallic system of Rh and Sn, e.g. Rh-Sn alloy, was formed at the higher temperature than 673 K. The obtained bimetallic surface was markedly active for CO oxidation reaction.

1. INTRODUCTION Supported Rh- and Ru-Sn catalysts have shown high activity for reduction of N O by CO [1 ]. Especially, the effective removal of N O was observed in 02rich atmosphere. The high removal of N O in the oxidative atmosphere was attributable to a cleaning effect of Sn in the bimetallic system by spillover of oxygen atoms adsorbed on Rh or Ru sites to Sn sites [2]. Recently, we have also reported that oxidation of CO over the silica supported Rh catalysts was enhanced by incorporation of Sn [3]. The temperature which CO oxidation

180 started was lowered by the addition of Sn [3]. These studies indicate that Sn is an effective additive in CO oxidation reaction itself as well as NO reduction. The XPS study [4] have indicated that the Sn in Rh-Sn/SiO2 was reduced in a lower oxidation state, may be in Sn 0 - Sn 2+. The reduced Sn plays a significant role in activation of 02 molecules [4]. Mixing state between Rh and Sn may be important for CO oxidation, because an oxidation state of Sn is strongly influenced by the adjacent Rh atoms. Preparation method and activation condition (temperature and atmosphere) seem to be very important to control the mixing state of the bimetallic system. Dautzenberg et al. [5] have reported the interaction between Pt and Sn over A1203. The TPR (temperature programmed reduction) of the oxidized Pt-Sn/A1203 indicated that the reduction of Pt and Sn was greatly affected in the presence of Sn. They have also reported that Sn was not completely reduced to metallic state over A1203. Burch has reported the details of TPR spectra of Pt-Sn/A1203 [6]. Srinivasan et al. [7, 8] have reported that the microelectron diffraction method in order to study micro crystals of Pt-Sn system on A1203 and SiO2. They have found the alloy formation on A1203 support by the micro diffraction method, whereas no peak was observed in X-ray diffraction powder patterns. These results suggest that the alloy formation between Pt and Sn is not so difficult even over A1203, which strongly interacts with Sn species and may stabilize the state of Sn2+. Even in those case, 70 % of Sn was not reduced to metallic Sn on A1203. The state of Sn was strongly affected by loading of Sn and Pt and condition of pretreatment, that is, atmosphere m~d temperature. Bacaud et al. have reported that the percent of reduction of Sn was strongly affected by the content of Pt and Sn [9]. The starting material of Sn and the preparation method were important for the reduction state of Sn as reported by Sexton et al. [10]. The silica is a suitable support for reduction of Sn species and alloy formation [10]. In our case, SiO2 support, the high content of Rh and Sn (5 wt% each), and 773 K of reduction temperature will bring about the reduction to metallic Sn and the alloy formation might be expected. In this paper, we report the detail of reduction behavior of Rh-Sn/SiO2 by temperature programmed reduction method. The reduction temperature was one of the important factors to control the oxidation state of Sn in Rh-Sn bimetallic system. The relationship between the reduction behavior of Rh-Sn system and the activity for CO oxidation is studied.

181 2. EXPERIMENTAL

2.1. Catalyst preparation The details of the preparation method of the catalysts was described in the previous paper [4]. Rh-Sn/SiO2 was prepared by a conventional impregnation method. The silica gel was co-impregnated with a mixed aqueous solution of Rh(NO3)3 (Nakarai Tesque Inc., Kyoto Japan) and SnC12 (Nakarai Tesque Inc., Kyoto Japan). Loading of Rh was at 5 wt% with respect to the support and Sn was introduced in unity of Sn/Rh atomic ratio. It was reported that the efficient Sn/Rh ratio was unity for activation of oxygen molecules [4, 11 ]. The catalyst precursor prepared above was activated by calcination in flowing air followed by reduction in flowing H2 at prescribed temperatures for 5 h, respectively for adsorption experiments and for CO oxidation reaction. For temperature programmed reduction, the precursor was used directly without any thermal treatment, that means as impregnated samples were used, in order to investigate effects of treatment temperature, given below.

2.2. Temperature programmed reduction (TPR) Temperature programmed reduction was carried out in a flowing H2 (5.14 vol%) diluted by N2 with a flow system equipped with a thermo balance (Model DGC-40, Shimadzu Co., Kyoto). A furnace in the thermo balance was controlled by the thermal analyzer DT-40 (Shimadzu Co., Kyoto). The catalyst precursor was calcined in a flowing air at a prescribed temperature for 0.5 h in the system, then the sample was cooled in the flowing air to room temperature. The carrier gas, N2 or H2/N2 mixture, was dehydrated by molecular sieve just before the TPR cell. The calcined precursor was heated in flowing H2/N2 mixture in a constant rate of 10 K/min. A typical heating pattern, the calcination was carried out at 773 K, is shown in Fig. 1. The obtained responses weight loss or gain (TG) and difference of temperatures between the sample cell in which the catalyst was placed and the reference cell in which the SiO2 support was placed (DTA) were accumulated in a personal computer, and were processed with a soft ware supplied by Shimadzu Co. (Kyoto, Japan). It should be noted that the weight of the sample was kept in ca. 25 mg in order to obtain precise and reproducible results.

182 calcination

873

air

I J

" ~

TPR

purge N2

~ 5.14 % H2 in N2----~ t

L_

Z~

673

e~

E 473 in

F-

0

I

30

..

I

;

,

I

90 60 Elapsed time / min

........

I

120

Figure 1. Typical heating pattern in the TPR experiment 2.3. Adsorption Adsorption capacity of the catalysts for H2 and CO was measured in a static vacuum system. The adsorption was carried out at room temperature in 10 kPa of each gas. The capacity was evaluated by the difference between total amount of adsorption and reversible adsorption. The absorption of H2 at 373 K over the calcined precursor at was also measured in the system.

2.4. X-ray diffraction powder pattern The mixing-state of supported Rh and Sn was investigated by X-ray diffraction powder patters. The X-ray powder pattern of the catalysts was obtained by using Ni filtered Cu-Ka.

2.5. CO oxidation Oxidation of CO was carried out in a closed circulation system. The catalyst was reduced again in a reactor in 13 kPa of H2 prior to the reaction. The reactant gas was 15.9 kPa of CO-O2 mixture, which molar ratio was two in CO/O2. The conversion of CO was calculated from decrease of total pressure in the system The reaction rate was evaluated by an initial rate method.

183

a\

pI~DTA i exO"

...J '~_ TG b

0.5 mg[

,~

/'X. DTA

DTA

0.5 mgI TG

l

c

273

1

373

I

473

I

573

I

673

I,

e

i DTA

I

773

Temperature

J

373

473

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573

i

673

773

/ K

Figure 2. TPR spectra o f Rh/Si02 and Rh-Sn/Si02 catalysts a: Rh/Si02 calcined at 773 K, b: Rh-Si02 calcined at 573 K c: at 673 K, d: at 773 K, e: at 873 K


3.1. Reduction behavior of Rh-SrdSiO2 Temperature programmed reduction spectra of Rh/SiO2 and Rh-Sn/SiO2 calcined at different temperatures were shown in Fig. 2. The spectnun a indicates a strong exothermic peak at 360 K over Rh/SiO2 (in DTA line) accompanying with the weight loss which began at 356 K (in TG line). This result indicates that

184 Rh oxide supported on SiO2 was reduced at c.a. 360 K. The spectra b to e show DTA-TG lines over Rh-Sn/SiO2. The DTA spectra indicate that two major peaks, one was sharp near 370 K, the other was a broad beyond 420 K. The first sharp peak was similar to reduction of Rh oxide over Rh-Sn/SiO2, which accompanied no weight loss (TG). The formed H20 was not desorbed from the catalyst below 400 K. The position of peaks in the DTA lines obtained over RhSn/SiO2 catalyst are summarized in Table 1.

Table 1 Temperature offirst DTA peak and weight loss stated Temperature first peak

Catalyst Rh/Si 02

773K,

Rh-Sn/SiO2

573K 673K 773K 873K 9 calcination temperature

360K

Temperature weight loss started 356K

395K 383K 400K 442K

469K 465K 442K 428K

The temperature of the first peak except the spectrum c, which was calcined at 673 K, tended to shift toward higher temperature with increasing calcination temperature as shown in Table 2 and Fig. 2. The reducibility of Rh oxide was lowered with addition of Sn. The H2-absorption capacity of the calcined catalysts at 773 K was measured at room temperature and 373 K in order to study the reducibility of the catalysts as shown in Table 2.

Table 2 H2-absorptionof Rh and Rh-Sn/Si02 Absorption temperature

room temp.

1st dose 2nd dose total 1st dose 2nd dose total

Amount of absorbed H2 rtmole/g-cat Rh/SiO2 Rh-Sn/SiO2 189 5.2 136 2.8 325 8.0 600 484 111 158 711 642

185 At room temperature, a significant amount of absorption was observed over Rh/SiO2, whereas no hydrogen was absorbed over Rh-Sn/SiO2 as shown in Table 2. At 373 K, 711 lamole/g of H2 was absorbed over Rh/SiO2, which was almost same as the theoretical value of H2 consumption to reduce Rh3+ to RhO, 694 ~tmole/g-H2 for 5 wt% Rh/SiO2. Over Rh-Sn/SiO2, the H2 consumption was 642 lamole/g, which was identical to the theoretical value to reduce only Rh3+ to RhO, 658 lamole/g. These results indicate that Rh oxide was more easily reduced to metallic Rh in Rh/SiO2 than in Rh-Sn/SiO2 and that the reduction peak in the range of 370-440 K in TPR spectra was ascribed to the reduction of Rh oxide in Rh-Sn/SiO2. No weight loss at 400 K in TPR spectra means that desorption of H20 from the catalyst required much higher temperature than the reduction of Rh oxide. The absorption experiment also indicated that H2 absorption was observed without H20 evolution at room temperature and 373 K over Rh/SiO2 and RhSn/SiO2. The calcination at a high temperature will result in a Sn-enriched surface of Rh-Sn/SiO2 because the aff'mity of Sn for oxygen is greater than that of Rh. The enrichment of Sn on the surface would suppress the reduction of Rh oxide. Butch [6] has also reported that the peak corresponding the reduction of Pt oxide in the calcined Pt-Sn/A1203 was shifted toward higher temperature with increasing Sn content. The second broad peak over 420 K was ascribed to the reduction of Sn oxide, which was accompanied by the weight loss. The weight loss corresponded not only to reduction of Sn oxide but also to the decrease of weight by the desorption of H20 which had been formed during the reduction of Rh oxide described above. Enough reduction of the calcined precursors were required reduction at 573 K as shown in Fig. 2. The weight loss was summarized in Table 3.

Table 3 Weight loss and corresponding oxygen eliminated

catalyst Rh/SiO2 Rh-Sn/SiO2

773K* 573K 673K 773K 873K 9 calcination temperature

weight loss (mg/g-cat) 15.8 39.9 38.9 23.2 14.8

corresponding 02 molecules ~tmole/g-cat 0.49 1.25 1.22 0.72 0.46

O/Rh (atomic ratio) 2.1 5.7 5.2 3.3 2.1

186 The corresponding eliminated-oxygen calculated from the weight loss was also shown in the table. The theoretical value of the O/Rh was estimated at 3.5 in order to reduce both Rh (III) and Sn (IV) to the corresponding metals. The larger values than 3.5 in Table 3 would be ascribed to the residual water which came from the cartier gas, although the cartier gas was dehydrated by molecular sieve just before the DTA-TG cell. The original adsorbed water on the catalysts would not affect the weight loss because the sample was calcined at 573 K before TPR experiment, which was higher than the desorption temperature (350-440 K) of H20 as shown in Fig. 2. The larger values observed over Rh-Sn/SiO2 than over Rh/SiO2 suggested that the significant amotmt of Sn in Rh-Sn/SiO2 was readily reduced to lower oxidation state, Sn (0). The previous paper [11] has also indicated that the reduced Sn/SiO2 at 773 K did not absorb oxygen during oxidation experiment at 773 K. Tin in Sn/SiO2 was hardly reduced at 773 K in H2 [11]. The TPR spectra of Sn/SiO2 (5 wt% of Sn) calcined at 773 K showed no reduction peak up to 773 K. These results indicate that the reduction of Sn oxide was catalyzed by the presence of an active component, Rh metal, that is, the spillover hydrogen which was formed on metallic Rh particles reduced the Sn oxide in Rh-Sn/SiO2 catalyst. Recently, Aranda et al. [12] have reported that the reduction of Sn was catalyzed by the presence of Pt over A1203. They have also found that ca. 28 % of Sn (IV) was reduced to Sn (0). The similar behavior was observed over Nb205 support [12]. In the case of A1203, the interaction between Sn and A1203 may be too strong to reduce Sn oxide to metallic Sn at 773 K completely. Our results indicate that a part of Sn in Rh-Sn/SiO2 is readily reduced to metallic Sn and some part of reduced Sn might be alloyed with Rh. Srinivasan and Davis have also reported the formation of Pt-Sn alloy on silica support by X-ray diffraction and electron micro diffraction [8].

3.2. Adsorption capacity The adsorption capacity of the catalysts were shown in Tables 4 and 5 for H2 and CO. Table 4 indicates the influence of reduction temperature on the capacity. The adsorption capacity for H2 and CO was drastically decreased by addition of Sn. Especially, the amount of H2 adsorbed decreased by 10 to 20, whereas CO decreased by 4. This result was ascribed that hydrogen molecules required at least two adjacent atoms of Rh to be adsorbed dissociatively. This is well known as an ensemble effect for bimetallic catalysts. The adsorption capacity of the Rh-Sn/SiO2 catalyst which was reduced at 873 K was larger than that reduced at 473 K twice for H2 and CO adsorption. Table 5 indicates the

187

Table 4 Effect of reduction temperature on adsorption capacity catalyst Rh/SiO2 Rh-Sn/SiO2

773K, 473K 573K 673K 773K 873K

H2 (~tmole/g-cat) 52.5 2.02 2.44 1.32 2.00 4.94

CO (~tmole/g-cat) 103.2 26.2 26.6 30.1 31.3 41.0

*reduction temperature

Table 5 Effect of calcination temperature on adsorption capacity catalyst Rh/SiO2 Rh-Sn/SiO2

773K, 573K 673K 773K 873K ,calcination temperature

H2 (~tmole/g-cat) 52.5 6.80 5.48 2.43 1.80

CO (lamole/g-cat) 103.2 56.8 42.6 26.6 18.3

influence of calcination temperature on the capacity. Both the capacity for H2 and CO was decreased with increasing calcination temperature. These results suggest that the higher reduction temperature brings about a Rh rich surface and that the higher calcination temperature brings about a Sn-rich surface. The Sn-enriched surface would suppress the reduction of Sn oxide itself as well as the reduction of Rh oxide as discussed above. The low value of oxygen consumption of RhSn/SiO2, calcined at 873 K, calculated from TPR spectra is ascribable to the Snenriched surface as shown in Table 3. It should be checked whether Sn affects the dispersion of Rh particles or not. We have already studied the effect of Sn addition on the dispersion of Rh by comparing the XPS intensity and the adsorption capacity of H2 and CO [ 11 ]. The relative XPS intensity of Rh3ds/2 to a monolayer catalyst was larger than the theoretical value calculated from the adsorption capacity of H2 and CO by the method of Kerkhof and Mouljin [13]. These results indicated that the decrease of the adsorption capacity of Rh-Sn/SiO2 catalysts was ascribed not to the increase of isolated Rh particle size, but to surface composition of Rh-Sn bimetallic

188 particles so called the ensemble effect and/or to chemical modification of Rh metals by adjacent Sn atoms so called a ligand effect.

3.3. X-ray diffraction powder pattern Figure 3 shows the X-ray diffraction powder patterns of Rh-Sn/SiO2 reduced at different temperatures. The catalyst which were reduced below 573 K showed no shift of Rh (111) diffraction peak as shown in Fig. 3-a. The reduction over 673 K brought about a shift toward lower diffraction angle, which indicates well-mixing between Rh and Sn [3, 4, 11 ]. The Sn oxide in the calcined precursor

Rh3S.n

Rh

5

. ...,.

(/I c . ,.....

c

cr l,.-,wl

I

38

I

I

40 /-,2 20 /deg.

I

44

I

I

38

I

I

I

40 42 44 20 1 deg.

Figure 3. (left) XRD patterns of Rh-Sn/Si02 reduced at various temperatures 1:873 K, 2:773 K, 3:673 K, 4:573 K, 5:Rh/Si02 at 773 K Figure 4. (righO XRD patterns of Rh-Sn/Si02 calcined at various temperatures 1:873 K, 2:773 K, 3:673 K, 4:Rh/Si02 at 773 K

189 was enough reduced around 573 K as shown in Fig. 2. The mixing between the reduced Rh and Sn is required much higher temperature. Figure 4 shows the XRD powder patterns of the Rh-Sn/SiO2 which was calcined at different temperatures followed by reduction at 773 K. The catalyst calcined at 673 K indicates both Rh and Rh-Sn structure. The calcination at a low temperature brought about the significant segregation of Rh and Rh-Sn. Although neither metallic Sn or Sn oxide was observed in the XRD patterns, a segregated Sn could not be excluded. 3.4. CO oxidation Figure 5 shows the CO oxidation activity over Rh-Sn/SiO2 catalysts which were reduced at different temperatures. The activity was evaluated with the apparent first order rate constant. The initial reaction rate for CO oxidation depended on partial pressure of 02 in first order over Rh and Rh-Sn/SiO2 described previously [3]. The dashed line indicates the activity over Rh/SiO2. The activity over the catalyst reduced at 573 K was identical to that over Rh/SiO2 as shown in Fig. 5.

~~' ,,"" 0"-0-0

1.0 T

cn

'I/i

0.5

0

'

D-ZS

373

'

'"' 0

~ '

'

'

423 Temperature / K

'

'

m

I

473

Figure 5. CO oxidation activity o f Rh-Sn/Si02 reduced at various temperatures O" reduced at 573 K, A: at 673 K, D: at 773 K The dashed line means the activity o f Rh/Si02 reduced at 773 K.

The catalysts reduced at 673 and 773 K indicated much higher activity at low reaction temperatures. The temperature which the activity appeared was lowered by 40-50 K. These results are well correlated to the peak shit~ in XRD powder

190 patterns as shown in Fig. 3. The well-mixing of Rh and Sn brings about the high activity at low temperatures of Rh-Sn/SiO2 for CO oxidation reaction. The surface composition and oxidation state would be changed from the state just after pretreatment because the catalysts were exposed to the oxygen containing atmosphere during the reaction, whereas only the metallic Rh phase (or Rh-Sn phase) was observed in the XRD patterns atter the reaction. The unusual temperature dependence of the CO oxidation as shown in Fig. 5 has been reported [14] and would be ascribed to the modified surface composition of adlayer, which was consisted of CO and O atoms, during the reaction discussed previously [3]. Although the change of the surface composition during the reaction seemed to be considered, the initiation temperature of the reaction would be affected directly by the original surface composition and electronic state. 3.5. State of Rh-Sn on SiO2 and CO oxidation activity The reduction behavior of Rh-Sn/SiO2 can be summarized below. 1)Rhodium oxide of the calcined catalyst was reduced first in the range of 360 to 420 K. 2)Tin oxide was reduced over 440 K with catalyzing by metallic Rh. 3)The alloying between Rh and Sn proceeded at a higher temperature than 673 K during the reduction. For CO oxidation reaction, the most important factor was the alloying between metallic Rh and reduced Sn, because the high activity of the catalyst required the reduction at higher temperature than 673 K as shown Fig. 5. The reduction up to 573 K may gave metallic Rh and the reduced low valent Sn (some part of Sn was reduced to Sn0), which was separated each other. The separated Rh and Sn indicated the same activity for CO oxidation as Rh/SiO2. The reduction at higher than 673 K would induce the mixing between Rh and Sn. The well-mixed Rh-Sn on SiO2 seems to be markedly active for CO oxidation.

191 REFERENCES

M. Masai, K. Murata and M. Yabashi, Chem. Lett., (1979) 989. M. Masai, K. Nakahara, K. Murata, S. Nishiyama, and S. Tsuruya, Stud. Surf. Sci. & Catal., 17 (1983) 89. S. Nishiyama, M. Akemoto, I, Yamamoto, S. Tsuruya, and M. Masai, J. Chem. Soc. Faraday Trans., 88 (1992) 3483. S. Nishiyama, H. Yanagi, H. Nakayama, S. Tsuruya, and M. Masai, Appl. Catal., 47 (1989) 25. F. M. Dautzenberg, J. N. Helle, P. Biloen, and W. M. H. Sachtler, J. Catal., 63 (1980) 119. 6 R. Butch and L. C. Garla, J. Catal., 71 (1981) 360. 7 R. Srinivasan, L.A. Rice, and B.H. Davis, J. Catal., 129 (1991) 257. 8 R. Srinivasan and B.H. Davis, Appl. Catal. A, 87 (1992) 45. R. Bacaud, P. Bussi6re, and F. Figueras, J. Catal., 69 (1981) 399. 9 10 B.A. Sexton, A.E. Hughes, and K. Foger, J. Catal., 88 (1984) 466. 11 S. Nishiyama, H. Yanagi, S. Tsuruya, and M. Masai, Proc. 2nd Intem. Conf. Spillover (Leipzig, 1989), (1989)pp 116-126. 12 D.A.G. Aranda, F.B. Noronha, M. Schmal, and F.B. Passos, Appl. Catal. A, 100 (1993) 77. 13 F.P.J.M. Kerkhof and J.M. Mouljin, J. Phys. Chem., 83 (1979) 1612. 14 G.K. Boreskov, in Catalysis, ed. J.R. Anderson and M. Bourdart, Springer-Verlag, Berlin, 1982, vol. 3, p.39.


A. Frennet and J.-M. Bastin (Eds.) Catalysis and Automotive Pollution Control Ill Studies in Surface Science and Catalysis, Vol. 96 1995 Elsevier Science B.V.

193

P R E P A R A T I O N OF Pt-Rh / A 1 2 0 3 - C e O 2 C A T A L Y S T S BY SURFACE REDOX REACTIONS L.Pirault a, D. El Azami El Idrissi a, p. Mar6cot a, J.M. Dominguez G. Mabilon c M. Prigent c and J. Barbier a.

b,

a Universitd de Poitiers. URA CNRS 350, Laboratoire de Catalyse en Chimie Organique, 40 Avenue du Recteur Pmeau, 86022 Poitiers Cedex, France. b lnstituto Mexicano del Petroleo, 1.A. Apdo Postal 14-805, Eje Central L. Cardenas 152, 07730 DFMexico. c

Institut Frangais du Pdtrole, 4-6 Rue du Bois Prdau, 92506 Rueil Malmaison Cedex, France.

ABSTRACT

9

Three-way automotive Pt-Rh catalysts were prepared either by coimpregnation of the two noble metals (C.I. catalysts) or by an original method of successive impregnations with a reduction step after platinum impregnation (S.I. catalysts) . It was shown that addition of rhodium can lead to opposite effects on the activity of platinum deposited on alumina-ceria for the reaction of propane oxidation, according to the preparation procedure 9the coimpregnation of the two metals induces an inhibition of platinum activity when the addition of rhodium by successive impregnations leads to the reverse effect . The differences between the two preparations are greater on oxidized samples after aging at high temperature (900~ These results are explained by the formation of alloy particles on coimpregnated catalysts while rhodium added by successive impregnations would be selectively deposited on surface cerium, avoiding the formation of Pt-Rh alloy. Energy dispersive spectroscopy fitted to a STEM unit allowed to bear out such hypothesis.


Typical commercial three-way catalysts contain both platinum for C O and hydrocarbon oxidation, and rhodium for N O reduction . However, an intimate

194

interaction between platinum and rhodium with alloy formation results in decreased activity for hydrocarbon or CO oxidation [ 1-4]. This detrimental effect is generally observed over platinum-rhodium bimetallic catalysts prepared by coimpregnation of the two noble metals. Indeed, this preparation procedure leads to alloy formation and to the enrichment of metallic particle surface with relatively inactive rhodium oxides after high-temperature aging under oxidizing conditions [ 1-8], resulting in poor oxidation activity. Recently, we developped a preparation procedure of bimetallic Pt-Rh/AI203-CeO 2 catalysts by an original technique of successive impregnations (SI) in the course of which rhodium deposition would occur by a redox reaction between surface cerium atoms and rhodium ions [9]. In this paper we investigated the properties of three-way automotive Pt-Rh / AI203-CeO 2 catalysts prepared either by simultaneous impregnation of the two noble metals (coimpregnation = CI) or by the technique of successive impregnations (S.I.). Their catalytic performances were measured after reduction or calcination at 500~ for the oxidation of a propane-propene mixture under lean conditions and for the reduction of NO by CO under stoichiometric mixture. Monometallic platinum catalysts and an alumina supported bimetallic platinumrhodium catalyst were also prepared for a comparative study.

2. EXPERIMENTAL

2.1. Catalysts preparation The supports used were a y-AI20 3 with a BET area of 100 m 2/g and the same alumina modified by addition of cerium chloride in order to obtain an alumina ceria with 12 wt % ceria after calcination at 450~ . Monometallic catalysts were prepared by impregnation of chloroplatinic acid. After drying, the different samples were calcined at 450~ and reduced under hydrogen at 500~ for 4 h and 8 h, respectively. Bimetallic catalysts were prepared by impregnation of chloroplatinic acid and rhodium chloride following two procedures : the first one was the classical coimpregnation of the support with aqueous solutions of platinum and rhodium salts (C.I. catalysts). After drying at 120~ the catalyst samples were calcined in air flow at 450~ for 4h, then reduced under hydrogen at the same temperature for 8 h . The latter method employs a two-step impregnation procedure (impregnation of platinum followed by impregnation of rhodium) with air-drying (120~ ovemight), calcination (450~ 4 h) and reduction (500~ 8 h) steps between successive noble metal impregnations (S.I. catalysts). Following final impregnation, the S.I. catalyst was dried in air ovemight at 120~ and reduced at 500~ for 8 h. The different catalysts were

195 either dechlorinated at 500~ for 10 h in a stream of N 2 + 10% H20 or thermally aged at 900~ for 16 h in a stream of 1% 02, 10 % H20, 10 % CO2, N2 and then reduced at 500~ The dechlorination treatment was carried out in order to avoid the inhibiting effect of chlorine on the activity of catalysts for hydrocarbon oxidation [10]. The chlorine content of dechlorinated samples was below 0.2wt%. Before activity measurements, catalysts were either reduced under hydrogen at 500~ or oxidized at the same temperature. Metal and ceria loadings of the different catalysts are reported in Table 1.

Table 1 Metal and ceria loadings of the catalysts (C1 9coimpregnated catalyst ; $1" catalyst prepared by successive impregnations). Catalyst Pt / A120 3 Pt / A1203-CeO 2 PtRh / A1203 (CI) PtRh / AI203-C~ (C1) ~ / AI203-CeO2 (SI)

Ceria loading wt% / 12.0 / 12.0 12.0

Platinum loading wt% 1.0 1.0 1.0 1.0 1.0

Rhodium loading wt% / / 0.1 0.1 0.1

2.2. Hydrocarbon oxidation activity measurements Hydrocarbon oxidation was performed in a flow reactor system equipped with a flame ionization detector (FID). The reactant mixture was composed of 0.2% propene and 0.2 % propane in N2 with 2 % oxygen (5 % excess oxygen). The gas flow rate was set at ca. 15000 ml h-1 . The catalyst weight was typically 50 mg diluted in 250 mg ot-ml20 3 . Catalysts were evaluated by studying their light-off behaviour with a constant flow of the gas mixture from 100 ~ C to 500~ at a heating rate of 3~ min-1. 2.3. Reaction of CO +NO Reaction of CO + NO was conducted in a flow reactor at a space velocity of 20000 h -1 with a stoichiometric mixture containing 2.0 mole % NO and CO in helium. Catalysts were evaluated by studying their light-off behaviour in temperature programmed experiments from 20~ to 500~ at a heating rate of 2~ min-1 . Before the catalytic run, catalyst samples were either calcined or reduced under H2 at 500~ for 2 hours. The analysis of the gas mixture was performed by gas chromatography using a CTR1 column provided by Alltech which allows to separate N2, NO, CO, N20 and CO2.

196

2.4. Elemental analysis (energy dispersive spectrometry EDS) All the microanalysis work was carried out in a JEOL-100 CX electron microscope fitted with a STEM unit, an X-ray detector and a Tracor-Northern5500 console . This system has a series of image processing routines such as filtering and particle recognition programs, as well as the standard programs and files for elemental analysis : SMTF and MICRO Q. The compositional microanalysis was done by bombarding a sample region with an electron beam at 40 kV, thus provoking X-ray emission which carries out both the characteristic radiation and the continuous backgrotmd from the region of interest. The X-ray signals which are generated in the microscope chamber are detected and transmitted by a Si / Li detector. The information is processed in the Tracor-Northem system. A typical spectrum is obtained in a couple of minutes from 0 to 40 keV ; in this energy region all the primary (K lines) or secondary (L,M,...lines) emission lines appear sharply. As each element of the periodic table has its own emission line family, a straightforward qualitative analysis may be done. The quantitative analysis requires a ft~her treatment of the data by means of the computer programs. This is usually done by use of the standard metallurgical thin film or the MICRO Q programs, which provide the atomic and weight percents. The EDS analysis may be done either from a relatively large region (average analysis) or from a 200 A-wide region (point analysis), therefore one can obtain the compositional fluctuation around an average value . All the analysis are based on the direct relationship between the intensity of the X-ray signal and the concentration of the element under analysis : I(A) / 103) = K(AB)C (A) / C(B), but in most of the cases a further correction is applied for absorption and fluorescence effects [11 - 13] . The following X-ray lines were used for analysis : A1 - KGt at 1.487 keV, Ce - Lot at 4.840 keV, Pt - L a at 9.441 keV and Rh - La at 2.696 keV).

3. RESULTS

3.1. Propane- propene oxidation Catalysts were evaluated by their light-off temperature in temperatm'e programmed experiments under lean conditions (5% excess oxygen). On dechlorinated samples, calcination at 500~ before hydrocarbon oxidation induces an inhibiting effect on ceria containing catalysts for propene oxidation (Fig l a) . On the other hand, the inhibiting effect of ceria appears already after reduction for propane oxidation (Fig 1b)

197 Light-off temperature *C 500

la

450

450

400

400

350

350

300

300

250

250

200

200 PtAI

PtAICe

,bj

Light-off temperature *C 500,

PtRhAICI PtRhAICeCI PtRhAICeSI Catalysts

i

i

PtAl

PtAICc

i

PtRhAICI

Catalysts

i ~ C c C I

i

PtRhAICcSI

Figure 1. Effects ofthe pretreatment at 500~ (calcination (@) or reduction ( 0 ) ) on the light-off temperatures of dechlorinated catalysts for propene (la) and propane (lb) oxidation.

9 Thus, dechlorinated catalysts exhibit the same activity for propane We must note also that the oxidation after calcination or reduction at 500~ catalytic properties of bimetallic PtRh / AI20 3 - CeO 2 catalysts are not affected by their preparation procedure. .

Light-off temperature *C

Light-off temperature *C

2a

550 500

500

450

450

400

400

350

350

300

300

250 200

1 PtAI

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P t R h A l CI

Catalysts

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2b

550

250 200

f

PtAI

i PtAICe

i R R h A I CI

i ~ C e

i CI R R h A I C e SI

Catalysts

Figure 2. Effects of the pretreatment at 500~ (calcination (@) or reduction ( O ) ) on the light-off temperatures of thermally aged (900~ catalysts for propene (2a) and propane (2b) oxidation.

On thermally aged catalysts, the pretreatment (calcination or reduction at 500~ does not affect catalyst activity for propene oxidation (Fig 2a) . On the other hand, the results reported in Fig 2b show that coimpregnated bimetallic platinum-rhodium catalysts endure an increase in their light-off temperature with respect to propane oxidation after an oxidizing treatment at 500~ . The same effect is observed when prereduced samples are submitted to a second oxidation cycle after a first cycle up to 850~ under lean conditions (Fig 3) . As for the

198 bimetallic platinum-rhodium / alumina-ceria catalyst prepared by successive impregnations, it exhibits the same activity for propane oxidation whatever the nature of the pretreatment (Figs 2 - 3). Lkjht-off temperature *C 550 500 450 ' 400 350 (3-

300 250

200 PtRhAI CI

I

I

PtRhAICe Cl

PtRhAlCe SI

Catalysts Figure 3. Effects of successive oxidation cycles under lean conditions on the light-off temperatures of prereduced thermally aged catalysts for propane oxidation ( o 9first cycle; 9 " second cycle" final temperature of the first cycle" 850~

3.2. C O + N O reaction

The activity of the different catalysts was evaluated by the temperatures at 50% conversion for NO and CO. The selectivity of NO reactions was characterized by the amount of NO transformed into N20 in the course of the temperature programmed experiment and by the temperature at 50% conversion of NO into N2. Light-off terr~rature =C

450

4

400 350 aoo

Light-off temperature *C 450

350

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150

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PtRhAICr CI PtRh,~Cc SI

100

1

PtAI

I

PtAICr

I

I

1

PtRhAI CI PtRhAICr CI PtRhAICr SI

Catalysts

Figure 4. Effects of the pretreatment at 500~ (calcination (o , 9 ) or reduction ( e , [--]) ) on the light-off temperatures of dechlorinated (4a) and thermally aged (4b) catalysts for NO reduction ( ~ , l---] ) and CO oxidation ( o , 9

199

A m o u n t of NO transformed into N20 mole * 10E-4/g of catalyst

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40

.

35

35

.

30

30

.

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25

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Amount of NO transformed into N20 mole * 10E-4/g of catalyst

_l PtAI

0 PtAICe

J PtRhAI CI

I P'.RhAIC 9 CI

0 PtRhAICe SI

Catalysts

Figure 5. Effectsof the pretreatmentat 500~ (calcination( 0 ) or reduction( ~ ) ) on N O formation by de,chlorinated(5a) and thermallyaged (900~ (5b) catalysts. 2 The results reported in Figs 4-5 show that the preparation procedure does not affect the catalytic properties of dechlorinated and thermally aged PtRh / AI20 3 - CeO 2 catalysts after initial calcination or reduction at 500 ~ C . Thus, these catalysts are generally more active than the monometallic catalysts or the PtRh / alumina catalyst for the CO + NO reaction. However, PtRh / A1203-CeO 2 catalysts produce more N20, particularly after a reducing pretreatment.

3.3. EDS microanalysis EDS microanalysis were conducted on thermally aged PtRh / A1203-CeO 2 catalysts prepared either by coimpregnation or successive impregnations. Table 2 gives the mean ratio of microanalysis of platinum and rhodium carried out on large particles (near 200 A) of the CI and SI catalysts. The results indicate that the particles examined on the SI catalyst contain only platinum while mainly bimetallic particles were observed on the CI catalyst. Moreover the analysis of the particle contour showed rhodium rich regions on the SI catalyst while platinum and rhodium were not detected in the vicinity of the large bimetallic particles on the CI catalyst (Fig 6).

Table 2 EDS m i ~ y s i s of metallic tx~cles on themu~ly aged C1 ~ CeO2 cz~ysts (CI : coimpre~'on ; SI : ~ i v e imprecations). Rh Catalyst PtRh / A1203-CeO 2 CI PtRh / A1203-CeO 2 SI

~ (mean atomic ratio) Pt 0.17 0.02

SI PtRh /A1203-

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4. DISCUSSION- CONCLUSION

The results presented in this paper indicate that ceria inhibits catalyst activity for hydrocarbon oxidation, particularly after an initial calcination step at 500~ This inhibiting effect of ceria can be explain by a charge transfer from precious metals to surface cerium resulting in higher oxidation state in the metals and therefore in lower activity [14, 15] . However, we must note that the inhibition of catalyst activity by ceria for propene oxidation disappears when the sample is reduced at 500~ before the catalytic run. For the reduction of NO by CO, dechlorinated catalysts are far less active after an oxidizing pretreatment at 500~ Thus, catalyst activity for the CO + NO reaction is also lowered when the oxidation state of the metals is higher. However the initial treatment (calcination or reduction) modifies the oxidation state of surface cerium (Ce 4+ or Ce 3+) which is involved in the CO + NO reaction [16 - 17]. Finally, the preparation procedure does not affect the catalytic properties of dechlorinated PtRh / A1203-CeO2 catalysts for the reactions studied in this work. The main differences between the two preparation procedures appear for propane reaction on oxidized thermally aged samples ( 1 % 02, 10 % H20, 10 %

201 CO2, N 2 , 900~ 16h). Thus, the activity of the PtRh / A1203-CeO 2 catalyst prepared by successive impregnations is not sensitive to the pretreatment before the oxidation reaction while coimpregnated PtRh catalysts are far less active when they are preoxidized at 500~ (Fig 2b). This result is in accordance with the conclusions of previous work [18] which state that, after oxidizing thermal aging, the coimpregnation would lead to the formation of Pt-Rh alloys with surface enrichment in relatively inactive rhodium oxides . On the other hand, rhodium added by successive impregnations, with a reduction step after platinum impregnation, would be selectively deposited on surface cerium in the vicinity of platinum particles, avoiding the formation of PtRh alloy. EDS microanalysis of thermally aged PtRh / A1203-CeO 2 catalysts bear out this conclusion since the large particles examined on the SI catalyst contain only platinum while mainly bimetallic PtRh particles were observed on the CI catalyst. ACKNOWLEDGEMENTS

This work was carried out within the "Groupement de recherche sur les Pots Catalytiques" funded by the "Centre National de la Recherche Scientifique", the "Institut Fran~ais du P6trole" and the "ADEME" (Agency for Environment and Energy Savings). REFERENCES

W.B. Williamson, H.S. Gandhi, P. Wynblatt, T.J. Truex and R.C. Ku, Aiche Symp. Ser. n 201, 76 (1980) 212. S.H. Oh and J.E. Carpenter, J. Catal, 98 (1986) 178. F.C. Van Delft, B.E. Nieuwenhuys, J. Siera and R.M. Wolf, Iron and Steel Institute of Japan Intemational, n~ 29 (1989) 550. I. Onal in "Catalyst Deactivation" (C.H. Bartholomew and J.B. Butt, Eds.), Amsterdam, (1991), 621. B.R. Powell, Appl. Catal., 53 (1989) 233. S. Kim, M.J. d' Aniello, Appl. Catal., 56 (1989) 23. S. Kim, M.J. d' Aniello, Appl. Catal., 56 (1989) 45. S. Kacimi and D. Duprez in "Catalysis and Automotive Pollution Control II" (A. Crucq, Ed.), Amsterdam (1991) 581 . P. Mar6cot, L. Pirault, G. Mabilon, M. Prigent and J. Barbier, Appl. Catal. B, 5, (1994), 57

202 10

P. Mar6cot, A. Fakche, B. Kellali, G. Mabilon, M. Prigent and J. Barbier Appl. Catal. B, 3, (1994), 283 11 J.M. Dominguez, G.W. Silmnons and K. Klier, J. Mol. Catal., 20 (1983) 369. 12 J.M. Dominguez mad D.R. Acosta, 8th Int. Congress on Catalysis, Berlin, (1984) DECHEMA, Vol 5, pp 287 - 298. 13 G. Del Angel, S. Alerarool, J.M. Dominguez, R.D Gonzales and R. Gomez, Surf. Sci. 224 (1989) 407. 14 Y.F. Yu Yao, J. Catal. 87 (1984) 152. 15 J.G. Nunan, H.J. Robota, M.J. Colin and S.A. Bradley, J. Catal. 133 (1992) 309. 16 B. Harrison, A.F. Diwell and C. Hallett, Platinum Metal review 32 (1988) 73. 17.G. Leclercq, C. Dathy, G Mabilon and L. Leclercq, in "Catalysis and Automotive Pollution Control II" (A. Cmcq, Ed.), Amsterdam, (1991), 181. 18 P Mar6cot, A Fakche, L Pirault, C. G6ron, G Mabilon, M. Prigent and J. Barbier. Appl. Catal. B, 5, (1994), 43

A. F rennet and J.-M. Bastin (Eds.) Catalysis and Automotive Pollution Control III Studies in Surface Science and Catalysis, Vol. 96 1995 Elsevier Science B.V.

203

REACTIVITY OF PEROVSKITES AS A U T O M O T I V E CONVERTERS

Laure SIMONOT, Franqois GARIN and Gilbert MAIRE Laboratoire d'Etudes de la R6activit6 Catalytique, des Surfaces et Interfaces, URA 1498 CNRS- ULP - EHICS, Institut Le Bel, 4, rue Blaise Pascal 67070 Strasbourg cedex, France

ABSTRACT The reactivity of three perovskites containing cobalt in three different oxidation states, Co(II), Co(III) and Co (IV) has been studied under two types of gas flow composition : i) binary mixtures containing either CO + 02, CO + NO or C3H8 + 02 . ii) a complete gas mixture with CO + C3H8 + NO + 02 . In both cases nitrogen was the balance gas. The reactivity order is found always to be the same, whatever the reaction : Co304 > LaCoO3/Co304 ~ LaCoO3 > BaCoO2.x > Ba2CoWO 6 , and is correlated to the reducibility of the samples followed by TPR. The first four catalysts exhibit the same reactivity for the CO + 02 reaction as classical Pt-A1203 and Pt-CeO2/A1203 catalysts, their light-off temperatures being between 430 and 500 K. These perovskites give reproducible results after the surface has been changed by the reactant gases, this phenomenon has been observed by the presence of a hysteresis, for Co304, under the CO + 02 gas mixture.

1. INTRODUCTION Since 1970 perovskite-type oxides (ABO3) have been suggested as substitutes for noble metals in automotive exhaust catalysts [1 ]. These oxides are efficient for oxidation reactions when for reduction the results obtained from the literature are dissimilar [2], mainly due to huge differences in the experimental conditions. The properties of perovskite-based catalysts are a function of the spin and the valence state of the metal in the B site cation, which is surrounded octahedrally by oxygen. The A site cation is located in the cavity made by these octahedra. For some perovskite-type oxides, their electronic structures have been pointed out to be similar to those of transition metals on the basis of theoretical

204 calculations and valence band structures [3-6]. Thus one of the catalytic features of these systems is to be active for hydrogen-involving reactions such as, for example, the hydrogenolysis of hydrocarbons [7]. As correlations have been observed, for catalytic oxidation reactions, between the activity and the electronic state of the transition metal [8], or the non stoichiometry of the perovskite [9], we have chosen, in our study, three perovskites containing cobalt in three different oxidation states, i) Co (II) in Ba2CoWO6 , ii) Co (III) in LaCoO3 , iii) Co (IV) in BaCoO3, and we have compared their reactivity with the spinel Co304. The aim of this study is to assess the catalytic behaviour of these perovskites as automotive converters.

2. EXPERIMENTAL

2. 1. Preparation of the catalysts All the catalysts have been prepared by a sol-gel method, starting from the oxide, acetylacetonate and carbonates : La203, Co(CH3COCHCOCH3)3, BaCO3, Co(CO3). Each precursor was dissolved in propionic acid, in such a way to get a concentration of 0.1 mol.dm-3, and mixed together in the desired proportions. For Ba2CoWO6, the ammonium metatungstate could not be dissolved in the propionic acid, and was thus suspended in this acid before mixing. After evaporation of the acid, the gel obtained was frozen, ground and calcined. All the calcinations were performed under air, with two temperature rates : one of 2 Kmin -1 up to 525 K, and the other of 3 Kmin-1 up to the final temperature, except for Ba2CoWO6 which was put directly in the furnace at 1225 K. Temperature and time of calcination are listed in Table 1.

2. 2. Characterization BET: the measurements were performed by the use of krypton at a temperature of 77 K with a Po = 3.276 mBar, the cross sectional area of krypton was taken equal to 19.5 A 2. All the results are listed Table 1. SEM: The average of the measured diameters of the particles are from 0.1 to 0.2 ml/1.

205

TPR/TPO measurements were obtained under 1.5% CO/He and respectively. Oxygen was analysed by thermal conductivity detectors and CO2 by IR. About 0.015 g of the catalyst was placed in a U-shaped reactor, and at a constant rate of 5 Kmin-1 under a gas flow of 40 cm3min-1 temperature to 1075 K. The results are discussed in the next section.

1% O2/He (TCD), CO was heated from room

X-RAY analysis:the identification of the catalysts by X-Ray diffraction (Ka Cr, D5000 Siemens) did not show phases other than those desired, i.e. perovskite or spinel phases. For BaCoO3 , the phase obtained is a non-stoichiometric perovskite, a mix between BaCoO2.8 and BaCoO2.x.

MICROANALYSIS was performed at Vemaison in the CNRS laboratory. The results obtained (table 1) showed a good stoichiometry in the perovskite phase between the ions in A and B sites, and gave us exactly the ratio between LaCoO3 and Co304 in the sample containing the two oxides : this ratio is Co/La = 2.7.

Table 1 Different characteristics of the catalysts Catalysts LaCoO3 LaCoO3/Co304 BaCoO2,x Ba2CoWO6 Co304

Calcination 1075 K 4 hours 1075 K 4 hours 1125 K 3 hours 1225 K 5 hours 1075K 4 hours

BET surface 3.2 m2g-1 3.3 m2g-1 1.5 m2g-1 1 m2g -1 2.6 m2g - 1

Microanalysis Co/La = 1.02 Co/La = 2.70 Co/Ba = 1.03 Co/W = 0.92 Co/O = 0.95 *

2. 3. Reactivity Testing The catalyst powder (0.8 g) was placed in a tubular quartz reactor. The composition of the gas flow was obtained by mixing the different components (CO, 02, NO, C3H8) diluted in N2 with the use of gas flowmeters. For all experiments the ratio (oxydant species/reductive species) was taken equal to 1. Before each reaction, the reactor is bypassed in such a way as to know precisely the composition of the gas flow before reaction.

* This ratio is surprising, by the fact its value is higher than for the pure stoechiometric oxide. But the X-Ray data doesn't show any other pick as for Co304. If there is an other phase (cobalt suboxide), this phase is not crystaUised.

206 The analysing section is composed of the following detectors: IR for CO, C3H8, and CO2, chemiluminescence for NO, paramagnetism for 0 2 . The experiments consist of increasing gradually the temperature with a rate of 4Kmin-1 and following the concentration of the gas flow. In all experiments, except when hysteresis reactions were performed, the catalyst was cooled under N2. When more information about the NO conversion was needed, we used a similar apparatus in which the analysing section is composed of three IR detectors for NO, N20, NO2. The composition of the other gases was determined by gas chromatography. Two sorts of gas flow composition were used: i) a binary mixture containing either CO + 02, CO + NO or C3H8 + 02 . ii) a complete gas mixture contaning CO + C3H8 + NO + 0 2 . All experiments were performed four times. The first one is considered as the activation process. The results given in the tables are an average of the three last experiments.


3.1 Temperature programmed reduction Figure 1 shows the TPR profiles for the three following compounds : Co304, LaCoO3 and LaCoO3 / Co304. We can observe the presence of one broad reduction peak at 640 K for Co304, in contrast two reduction peaks appear for the two other compounds; their reduction temperatures are 640 K and 750 K for LaCoO3 / Co304 and 720 K and 855 K for LaCoO3. The presence of metallic cobalt at the end of the experiment was verified by X-ray diffraction. In LaCoO3 we can observe that one cobalt species is more difficult to reduce. The last TPR peak appears at 855 K and can be attributed to an hindered reduction process of the cobalt due to the close presence of lanthanum oxide. This peak is shifted to lower temperature for LaCoO3 / Co304 because less lanthanum oxide is present in this sample, and finally for Co304 only one peak appears shitted by 80 K towards lower temperature. For Co304 similar results were obtained by Arnoldy and Moulijn [10]. They observed one sharp reduction peak for Co304 at 595 K, the TPR experiment was performed under hydrogen at a temperature rate of 10 Kmin -1. In our case we observed one reduction peak in the same range of temperature. For the perovskite, two reduction peaks were formed corresponding to Co ( I I I ) - - > Co (II) and Co (II) ----> Co (0), as already observed by Crespin and Hall [11 ].

207

For BaCoO2.x TPR cannot be interpreted due to carbonation of this perovskite under CO. For Ba2CoWO6, the TPR showed a little CO consumption at 655 K and can be related to adsorption-desorption phenomena.

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480

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610 740 T e m p e r a t u r e in K

LaCo03 LaCoO3/Co304 870

1000

Figure 1 : CO consumption in TPR experiments as a function of the temperature in K. The scale for the consumption is related to the ppm of CO consumed per mole o f cobalt m the catalyst.

3. 2 Temperature programmed oxidation The X-ray diffractions performed in a Guinier chamber (Ka Fe) have shown that, in all cases, TPO experiments performed after a TPR reproduced the initial compound. Only one oxidation peak was observed at 625 K for LaCoO3 and LaCoO3 / Co304 and at 725 K for Co304, no significant peak was observed for Ba2CoWO6.

3. 3 Catalytic activity under binary mixtures The results are listed in Tables 2a, 2b and 2c, and illustrate the temperatm'es at which the conversion, calculated on the basis of the disapearance of the polluant, is equal to 10%, 50% and 90%.

208

Table 2a Temperature of 10% conversion in binary mixture (K)

Co304 I.aCOD3/Co304 LaCoO3 BaCoO2.x Ba2CoWO6

CO + NO TlO NO 385 445 445 495 645

Tlo CO 415 485 520 525 655

CO + 02 TlO CO 385 405 410 425 475

HC + 02 TlO HC 490 520 550 635 680

Table 2b Temperature of half conversion in binary mixture (K)

Co304 LaC_oO3/C~O4 LaCoO3 BaCoO2.x Ba2CoWO6

CO + NO T5o NO 480 570 615 660 760

Tso CO 545 595 600 640 770

CO + 02 TSO CO 430 453 440 475 525

HC + 02 Ts0 HC 550 595 640 775 855

Table 2c Temperature of 90% in binary mixture (K)

Co304 I.zCO33/C~O4 LaCoO3 BaCoO2.x Ba2CoWO6

CO + NO T90 NO 545 745 710 765 865

T90 CO 590 640 640 700 885

CO + 02 T90 CO 450 470 450 490 575

HC + 02 * T80 HC 590 670 730 < 80% < 80%

* for HC we do not reach more than 85% conversion, the results listed are for 80% conversion, when it was reached.

209 From these tables we can observe the following points : The reactivity order is always the same, whatever the reaction and conversion, Co304 > LaCoO3/Co304 ~ LaCoO3 > BaCoO2.x > Ba2CoWO6. The two latter compotmds have very small TPR peaks, implying low oxygen mobility, which may explain in part their low reactivity. - Concerning the two oxidation reactions i.e CO + 02 and HC + 02, the former occurs at the lower temperature than the latter. The CO + NO reaction takes place in between these two ranges of temperature. - In the CO + NO reaction, the NO transformation is faster than the CO oxidation. To understand this point we have performed the experiments on the apparatus where IR detectors for NO, N20 and NO2 are present. We have noticed that the NO reduction does not give directly N2 but rather N20, as can be seen in figure 2. - When we compare the oxidation temperatures for CO in the CO + 02 and CO + NO reactions, we notice that the temperature is always lower in the former reaction. NO might be a poison of these catalysts, but on the other hand the apparent activation energy for CO + NO is higher than for CO + 0 2 . From the work by Oh et al. [12] on rhodium catalysts they noticed that the apparent activation energy for CO + 02 was equal to 14 kcal/mol and was lower by 17 kcal/mol than for CO + NO reaction. Halasz et al. [13] observed an apparent activation energy of 13 kcal/mol for the catalytic oxidation of CO over Co304. These results may suggest that the same slow step occurs on rhodium and Co304, and it was observed that the surface oxides can be formed either on Rh(111) or on supported rhodium, when they are treated under an oxidising environment [ 14,15]. From these results we can observe that Co304 is the more reactive system, but we notice that this oxide is the only one to be modified after the activation step. This modification was observed by XRD, and we showed the presence of two oxides : CoO and Co304. This result led us to study this oxide more carefully. 3 . 4 Co304 r e a c t i v i t y One question which may arise in these experiments concerns the reversibility* of these reactions. We studied the CO + 02 reaction by increasing and then decreasing the temperature under the same gas mixture. In figure 3 we * The term reversible has to be taken w i t h care. In o u r case it does not i m p l y the t h e r m o d y n a m i c reversibility.

210 can see the presence of a hysteresis loop. After rettmaing to room temperature, the next experiment follows the first curve obtained when the temperature was increased.

4000

""'' "

&

I....

N~ I N20

O U O

9

U

, ....

300

"

400

500 600 Temperature in K

I

i

-ii

700

800

Figure 2 9CO + NO reaction over LaCo03/Co304

20(0X)

I c~

fz~

&

~0 v..~

U 0

k9 I

0 250

350

I

450 ~i50 Temperature m

650

Figure 3 9Hysteresis experiment f o r C o 3 0 4 under the binary mixture CO + 02

211

Similar behaviour is also observed when the return to room temperature occurs under nitrogen instead of being performed under the reactive gas.. This result points out that either two different sites may exist at the surface, their presence being a function of the reaction temperature, or the nature and the amount of the adsorbed molecules are different versus the reaction temperature This phenomenon has also been observed with alumina supported catalysts, and rules out the hypothesis that hysteresis is related to a change in the oxidation state of the cobalt

20000

Initial concentration of CO

II 9

9

.... C02

v

o 9

t~

9

9

9

9

9

9

~

9

CO

f o

0 300

350

400 450 Temperature m K

500

Figure 4 9The C O + 0 2 reaction over C o 3 0 4

To confirm this idea we increased the cooling rate of the catalyst. At the end of a CO + 02 reaction, when the catalyst was at 573 K, it was rapidily cooled to room temperature in ten minutes under N2 and put again in contact with CO + 02, the CO concentration being 18 000 ppm. We have observed that this oxide was able to transform CO ~ > CO2 at room temperature with a conversion of 50% as shown in figure 4. This result may be explained by the quenching of the high temperature surface sites.

212

3. 5 Catalytic activity under the complete gas composition The results are listed in table 3, and show the temperature at which the conversion is equal to 50%.

Table 3 Temperature of half conversion in complete mixture (K)

Co304 I_aCcO3/Co304 LaCoO3 BaCoO2,x Ba2CoWO6

Ts0 NO Ce4+-O= + Ce4+-~ + N20

(3)

The resulting reoxidized Ce ions can act as new NO adsorption sites, leading e.g. to the formation of new chelating nitrites. Nitrates can conceivably be formed, on the other hand, by many different paths, most of them involving transformation of nitrite species and, in some cases, with electron transfer to the underlying oxide" 2 NO2 --+ NO3" + NO" NO2- + O- + 2 NO --+ NO3" + N202 =

NO2- + N20 --+ NO3" + N2 Ce4+-(NO2) + Ce4+-O = --* Ce3+-(NO3) + Ce3+-[--I c e a + - ( N O 2 ) + Ce4+-(ONNO)--Ce 4+ ~ Ce4+-(NO3) - + Ce3+-[ --] + ( N 2 0 . . C e 3+

(4) (5) (6) (7) (8)

In the case of CeO2/A1203, nitrites and hyponitrites (at least, of the t r a n s kind) are also formed by NO adsorption (2d); the formation of nitrates and c i s hyponitrites could not be ascertained, because of the low IR transmission by the alumina support in the range below 1050 em 1 (not depicted in 2 for the spectrum of this sample). It was however possible to observe that N20 (both adsorbed and in gas phase) was formed in rather smaller amounts than for CeO2, suggesting that c i s - N 2 0 2 = are formed in this case in lower amounts; the reason for this could be a need of higher proximity of associated vacancies, i.e. a higher concentration of them than available on dispersed CeO2, for generating the c i s form.

3.4. Temperature-programmed desorption after NO adsorption NO adsorption/thermodesorption tests were made by contacting the samples (previously subjected to the above mentioned standard treatment) with a NO:N2 stream (0.7% NO v/v, 750 cm3/min flow rate) at room temperature during 1 h, followed by briefly purging with N2 (5 rain) at the same flow rate and heating under the same N2 flow at a 12.5 K/rain rate up to 800 K. The amounts of evolved gases detected during such TPD run for samples A (Ce 02), C (I 0% Ce 02/ A1203) and D (pure A1203), using a 10 ml volume of catalyst (corresponding to sample quantities of 15.0, 6.2 and 5.5 g respectively), are plotted against temperature in 4a-c. These plots show that, for Ce 02 (Figure 4a), significant NO evolution is observed in three distinct peaks, centered respectively around 350, 550 and 770 K. N20 is detected in much smaller amount, an initial desorption tail is just hinted at the beginning of the experiment, followed some 100 K later by a small, broad peak. On the contrary, 02 and NO2 are clearly evolved nearly in coincidence with the high-temperature NO desorption peak. The behaviour of

223 sample C (Figure 4b) is similar, except that the first NO desorption peak is just barely discemable as a small shoulder, and the proportion of N 02 evolved in the high-temperature region is larger. Sample B (data not shown) behaves rather similarly to sample C, although a more noticeable NO desorption peak appears around 350 K, and the proportions between the products appearing in the high temperature range are intermediate between those of the A and C samples. In the case of the pure alumina (sample D, Figure 4c) the intermediate NO desorption peak is again observed, plus the set of desorption processes above 600 K in which the N O2/NO proportion is larger than in any of the preceding cases. The various features observed in these data must correspond to the stability or reactivity of the different surface species generated upon NO adsorption on the samples. Easiest to interpret are the desorption peaks observed at T3 673 K; because of the evolution of both NO2 and 02 (together with NO), this can only be interpreted as due to the decomposition of surface nitrate species, which can form both on CeO2 and on AI203. The higher NO/NO2 proportion observed in presence of cerium corresponds probably to the existence, in the stages previous to the beginning of this desorption peak, of a certain amotmt of Ce3+ which can be reoxidized in the process, decreasing the amount of NO2 liberated. On the other hand, the intermediate peak includes most probably the decomposition of nitrites, which appear also easily on both types of oxides. On a support with scarce redox capability such as alumina, where this process is clearly observed, the disproportionation of nitrites into NO and nitrates is the most likely reaction to explain this feature, since, to our knowledge, the formation of surface species containu~g N fi~ low (formal) oxidation degree, such as hyponitrites, upon NO adsorption has not been reported to occur in substantial amounts. Where ceria is present, other nitrite reactions can occur, grouped around the same temperature (corresponding to that of N-O bond breaking in NO2) but involving perhaps Ce 3+ and/or hyponitrite groups (which have been clearly detected on this oxide by IR); indeed, on sample A this desorption peak appears broader and with some incipient shoulder in the high-temperature side. As to the NO desorption peak observed below 373 K, which appears only for sample A, it is reasonable to relate it with other specific observations on this sample. In particular, this sample was the o~y one able (if pre-outgassed at T~3 473 K) to produce atter NO adsorption at room temperature N20 species (and, in fact, a taft of the desorption of this molecule can be detected at the beginning of the plot in 3a), the generation of which on ceria has been observed to coincide with the observation of the less stable cis-hyponitrite form. It seems therefore that the difference may lie in

224

I

CONCENTRATION (% moo . . . .

,8

~

,4

.

1,2

i

j

:

i

i

CONCENTRATION (% mol) -----~.

.

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i

0,8

-

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.

-

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:

0,4 ,2

i

0 300

4o0

soo

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7oo

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0 300

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soo

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600

7oo

800

TEMPERATURE (K)

CONCENTRATION (% moO

CONCENTRATION (% mol) 1,2~ ' ' '

0,4 0,3

(b)

0,2

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~

:

i

'

!

500

600

700

800

0,1 0 300

400

500

600

700

800

0 300

400

TEMPERATURE (K)

TEMPERATURE (K)

CONCENTRATION (%moo 0,5t

1,2 1

0,4 0,3

CONCENTRATION (% tool)

"

.

.

.

500

600

..

"=

0,8 (c)

0,6 - ( c )

0,2

0,4

0,1 300

0,2 400

500

600

700

800

TEMPERATURE (K) - " % CO

"+'% CO 2

% NOx2

0

300

.

.

400

.

.

700

-

"

800

TEMPERATURE (K) "'" % N 2 0 x l O ~ % NO 2 xlO -t-. % 02x2

Figure 4 ~ of(a-c): TPD aflerNO adsorption at 295 K," (A-C): TPRea~on with CO + NO + 02, obtainedfor (_,4,a): Ce02; (B,b): 10% CeOf A1203; (C,c): A1203.

225 the higher capacity of pure ceria (in comparison with the other samples), when thermally pretreated at 573 K or above, to activate more deeply at low temperature the NO molecule so as to generate unstable N202- species which decompose easily into N20. This in turn can be related to the ESR data, showing that associated anion vacancy sites, of the kind giving the O2 signal Oa upon 02 adsorption, are detected only for sample A. An interesting conclusion thus appears: the higher ability to activate reductively NO (and perhaps other molecules also) even at low temperatures depends on the capability to form these associated vacancy sites, which may exist on pure CeO2 but be more difficult to generate on CeO2/A1203 supports when ceria is well dispersed on the alumina substrate. 3.5. Temperature-programmed reaction experiments The catalytic activity of the samples was probed also in a temperatureprogrammed way. In this case, after the standard pretreatment, a gas mixture containing ca. 1% CO, 0.45% 02 and 0.1% NO in the N2 carrier (i.e. of stoichiometric redox composition) was fed on the sample at a rate equivalent to 104 h ~ space velocity; after a short time (3 rain) on stream (in order to ensure a steady gas flow on the catalyst), heating of the oven at a 10 K/rain rate up to 800 K was started. The concentrations of the different gases measured at the reactor outlet for the A, C and D samples are plotted against the sample temperature in Figure 4A-C. These results show that, while for pure alumina CO and 02 begin to be consumed in a quite parallel way, and CO2 is produced (as corresponds to a process dominated by CO combustion), at temperatures around 670 K, for the Ce-containing samples the same process begins at distinctly lower temperature, which is nearly the same for the different samples (540 K), indicating that the onset of the CO combustion process is catalyzed by ceria in a relatively similar way in the different samples (although it is enhanced at higher temperatures fia the pure CeO2, probably due to the higher total amount of exposed ceria surface present in this case). The NO profile is more complex. It is noteworthy that, for sample A, NO is not detected at the beginning of the temperature rise (even though it is present in the feed gas), which means that even after the initial interval of contact between the sample and the reacting mixture the NO molecules introduced are still being completely adsorbed by the sample, no other gas composition change being observable. NO does appear a T > 380 K, its concentration rising for a significant time above that of the incoming gas, which evidences clearly a substantial desorption of the initially adsorbed NO. For sample C, although such features of initial consumption and subsequent desorption of NO are less marked, they can be still clearly ascertained; actually, they appear to a small extent even in sample D. ha the cases of samples B-D such NO adsorption/desorption phenomena (observed in the range T < 700 K) seem

226

however to occur without significant involvement of CO in the process; the absence for sample C of the high-temperature peaks associated to decomposition of nitrate species suggests therefore that CO (which is not completely consumed in this experiment) may be acting at these higher temperatures to block the evolution of NO2 and 02 (a process in which the ceria component would be an active catalyst, since for pure alumina the NO2 and 02 evolution peaks, revealing the presence of nitrate groups, are still observed). The mentioned evolution of NO to give concentrations in the gas flow above those in the incoming gas is observed to occur for sample C in a broad range betweeen 473 and 673 K; this coincides with the range for NO evolution due to nitrite decomposition observed in the TPD runs. For sample A, however, the extra NO evolution in this range appears split in two peaks. This splitting might be related to the small additional decrease in the CO concentration which can be observed around 500 K for this sample but not for sample C. On the other hand, the marked fall in CO concentration and simultaneous NO evolution observed around 600 K for sample A suggests that a reduction of NO2- by CO may be operating at this stage. In any case, the elucidation of the nature of the transient steps in this temperature range is not straightforward, and may need fi~her experiments in order to be adequately clarified. Finally, at temperatures above ca. 750 K the NO concentration falls again below that in the feed gas, coincidently with the high level of consumption of CO. The new burst of NO evolution which still appears for sample A around 723 K together with production of some 02 and NO2 (clearly visible also for sample D) will be due to nitrate decomposition, and as said above indicates that, both on pure ceria and on alumina, surface nitrates can withstand the reaction conditions of this experiment up to temperatures of 700 K; in the first case, because previous reaction has completely depleted the gas stream from the reductant CO, and in the second one probably because of the low catalytic activity of A1203 against NO reduction. Reactivity seems thus to be in general rather smaller for the supported ceria samples than for the pure CeO2 (the TPD and TP reaction data of sample B, not shown in the figure, although intermediate between those of samples A and C are much closer to those of the latter specimen).

ACKNOWLEDGMENTS

The authors thank the CICYT (project nr. MAT91-1080-C03-02) and the EEC SCIENCE program (contract nr. SCI-CT91-0704 TSTS) for financial support given to this work, and to Prof. G. Munuera for providing a CeO2

227 sample. A. M.-A., J.M.C. and R. C. give thanks respectively to Comunidad de Madrid, the PFPI program and CSIC for Plff) fellowships, trader which their contributions to this work were carried out. Prof. L.A.P. gives thanks to the Spanish Ministerio de Educaci6n y Ciencia for support to a sabbatical year leave. References

1. a) G. Leclercq, C. Dathy, C. Mabilon and L. Leclercq, in A. Crucq (ed.), Catalysis and Automotive Pollution Control II (Stud. Surf. Sci. Catal. vol 71), Elsevier, Amsterdam, 1991, p. 181; b) B. Harrison, A.F. Diwell and C. Hallett, Plat. Met. Rev., 32 (1988) 73. 2. J. Sofia, A. Martinez-Arias and J.C. Conesa, Vacuum, 43 (1992) 437. 3. a) J. Sofia, A. Martinez-Arias and J.C. Conesa, submitted for publication. b) A. Martinez-Arias, Plff) Thesis, Universidad Autdnoma de Madrid, 1994. 4. J. Soria, A. Martinez-Arias, J.C. Conesa, A. Munuera and A.R. Gonzfilez-Elipe, Surf. Sci., 251/252 (1991) 990. 5. N. K~inzig and M.H. Cohen, Phys. Rev. Letters, 3 (1959) 509. 6. M. Che, J.F.J. Kibblewhite, A.J. Tench, M. Dufaux and C. Naccache, J. Chem. Soc. Faraday Trans. 1, 69 (1973) 857. 7. A. Martinez-Arias, J. Soria, J.C. Conesa, R. Catalufia, A. Arcoya and X.L. Seoane, in preparation 8. J.H. Ltmsford, J. Chem. Phys., 46 (1967) 4347. 9. E.L. Kugler, A.B. Kadet and J.F. Cryder, J. Catalysis, 41 (1976) 72. 10. M. Niwa, Y. Furukawa and Y. Murakami, J. Coll. Interf. Sci., 86 (1982) 260. 11. L. Cerruti, E. Modone, E. Guglielminetti and E. Borello, J. Chem. Soc. Faraday Trans. 1, 70 (1974) 729. 12. G. Busca and V. Lorenzelli, J. Catalysis, 72 (1981) 303. 13. C. Morterra, F. Boccuzzi, S. Coluccia and G. Ghiotti, J. Catalysis, 65 (1980) 231.


A. Frennet and J.-M. Bastin (Eds.) Catalysis and Automotive Pollution Control I11 Studies in Surface Science and Catalysis, Vol. 96 9 1995 Elsevier Science B.V. All rights reserved.

229

MECHANISM OF CHEMICAL ACTIVATION OF Pt-Rh ALLOY AND Pt/Rh BIMETALLIC SINGLE CRYSTAL SURFACES Hiroyuki Tamura*, Akira Sasahara and Ken-ichi Tanaka The Institute for Solid State Physics, The University of Tokyo 7-22-1 Roppongi, Minatoku, Tokyo 106 *KAO Corp. Wakayama Research laboratory, Wakayama 640

ABSTRACT

Pt0.25Rh0.75 (100) alloy, and Pt/Rh(100) and Rh/Pt(100) bimetal surfaces underwent chemical restructuring at T > 400 K by heating in ca. 10-7 Torr of NO or 02, and the surfaces were covered with a common hybrid overlayer of Rh-O/Pt-layer. The Rh-O/Pt-layer gives a characteristic p(3xl) LEED pattern and is active for the reaction of NO + H 2. As a result, PtRh(100) alloy and Pt/Rh(100) and Rh/Pt(100) bimetal surfaces have almost equal catalytic activity. Pt(110) surface was poorly active compared to Pt(100) surface for NO + H 2 reaction, but it was shown that Rh/Pt(ll0) and Rh/Pt(100) have almost equal catalytic activity. Therefore, it is concluded that a common Rh-O/Pt hybrid overlayer prepared by chemical restructuring is responsible to the prominent catalytic activity of the Pt-Rh catalysts for NO x reduction.


Catalytic reactions on metal surfaces are often remarkabily influenced by foreign metals. The Pt-Rh catalyst used for automotive exhaust gas control is a typical exmnple. The Pt-based catalyst is markedly improved by adding Rh, but the roles of Rh are still controversial. In order to throw light on such fimdmnental problems, we studied the adsorption of NO mad the reaction of NO with H 2 on Pt-Rh(100) alloy surface [ 1,2,3 ]. The catalytic reaction of NO with H 2 may be discussed by dividing into the following two steps.

230 i) NO + H 2 --N(a) + H20 ii) N(a) + H 2 --- NH3, N 2 When the first step i) is rapid but the step ii) is slow, N(a) intermediates will be accumulated on the catalyst surface. In fact, when NO + H 2 reaction was performed on Pd(100) and Rh(100) surfaces, accumulation of N(a) intennediates occurs on theses surfaces although Pd(100) and Rh(100) surfaces are inactive for the chemisorption of N2 [1,4]. However, no accumulation of N(a) intermediates was attained on Pt(100) and on Pd(110) surfaces although they catalyze the NO + H 2 reaction. It is noteworthy that the accumulation of N(a) does not occur on Pd(110) surface but it does on the Pd(100) surface [4]. This fact may suggest that NO + H 2 reaction will be a structure sensitive reaction. Taking these results into account, the question is really interesting whether N(a) intennediates are accumulated on Pt-Rh(100) surface or not [ 1,2,3]. A layerby-layer maalysis of a Pt-Rh alloy tip surface by atom probe FIM showed that the alloy surface almealed at 700 C is composed of a Pt enriched topmost layer and Pt depleted 2nd layer but Rh enriched 2nd layer [5]. Therefore, Rh atoms are mainly extracted from the 2nd layer by reacting with oxygen and make an ordered arrangement on Pt enriched layer, which is the origin of the characteristic p(3xl) LEED pattern [3]. That is, such a hybrid surface as Rh-O/Pt-layer may be responsible for the p(3xl) pattern on the Pt-Rh(100) surface[6,8]. It should be pointed out that the Pt enriched layer may not be disturbed by diffusion at T < 900 K [7], so that the Pt-layer will be fixed during the catalysis at around 500 K. If this hybrid surface model is acceptable, the same p(3xl) surface should be fonned on Rh deposited Pt(100) surface. In fact, we got a very sharp p(3xl) LEED pattern on Rh/Pt (100) surface by heating in NO or 02 at 400 K [8]. In this paper, it wil be shown that a common hybrid surface composed of Rh-O/Pt-layer given by chemical restructuring is responsible to the prominent activity of the PtRh catalyst for NO reduction.

2. EXPERIMENTAL

Electrochemical deposition of Pt ion on Rh(100) and Rh ion on Pt(110) was perfonned in a small volume cubic cell branched out the UHV chamber. Rh(100) and Pt(100) surfaces were subjected to a cleaning procedure consisting of Ar ion sputtering, 02 treatment (5xl 0-8 Torr ) at 800 - 1000 K for 10 min, and almealing at 1000 - 1200 K for 20 min. After the cleaning, the crystal was transfered into a cubic cell for electrochemical deposition. The cell was filled

231 with one atmospheric pressure of Ar gas, and then an electrochemical glass cell with electrolite solution of 0.05 M H2SO 4 + 5x10 -5 M PtC14 (or RhC13) was lifted up to make contact with the one side of the crystal disk. After the deposition of Pt or Rh ions, the crystal was washed with highly pure water and was transfered back to the UHV chamber for characterization by LEED and XPS as described before [8]. After the characterization of the surface, the sample was transfered again into the cubic cell for the reaction and/or! adsorption.


Pt and Rh atoms may be randomly distributed on Pt-Rh alloy surfaces, but the depth distribution of Pt and Rh atoms depends strongly on the am~ealing temperature. So far, it has been accepted that the higher the amaealing temperature, the higher the surface enricl~nent of Pt atoms. In fact, layer-by-layer analysis of a Pt-Rh alloy tip almealed at 700 C ( ca. 1000 K) showed Ptelmcl~nent on the topmost layer and Pt-depleted (Rh-enriched) 2nd layer [5]. However, a careful experiment performed on a Pt0.25Rho.75(100) surface showed opposed result between 950 K and 1300 K. That is, the Pt fraction of the surface is lowered by raising amaealing temperature, and it takes ahnost bulk composition at 1300 K [7]. It was also ponted out that the Pt-Rh(100) surface hardly attains to equilibrium distribution at T < 900 K. Therefore, annealing at higher T than 950 K is required to get equilibrium distribution of Pt and Rh atoms on Pt-Rh alloy surface. In contrast to this, chemical restructuring proceeds easily even at ca. 400 K by NO or 02 [2,3]. This fact suggests that the chemical restucturing is an unambiguously important process which should be generally considered on metals as well as on alloy surfaces during catalysis. Rh deposited Pt(100) surface gives very sharp p(3xl) LEED pattern when it is heated in 10 -7 Torr of 02 or NO at T > 400 K [8]. From this fact, it was deduced that the Pt-Rh(100) alloy surface giving p(3xl) structure may be covered with the same hybrid stucture as Rh-O/Pt-layer on Rh/Pt(100) surface. In order to confirm the chemical restructuring, Pt deposited Rh(100) surface (Opt = ca. 4 monolayer) was mmealed in 02. Segregation of Rh atoms took place by heating in lxl0 -7 Torr of O2 at 780 K as s h o w n in Fig. 1. As increasing the fraction of Rh on the surface, LEED pattern changed from c(2x2) to p(3xl) pattern.

232

. c(2x2)~,~ N

p(3xl)+p4gp(2x2)

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"13

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\

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v

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0

I

,

20

02

I

40

,

I

60

,

|

9

80

|

|

100

120

exposure time (min)

Figure 1 Segregation of Rh atoms on Pt/Rh(lO0) bimetallic surface by heating in 02 of lxlO -7 Torr at 780 K. LEED pattern at 60 eVshowsp(3xl)+p4g spots. It is interesting that formation of the p(3xl)on the Rh/Pt(100) surface (0Rh = 0.4 - 1.0 monolayer) took place far more rapidly compared to that on the Pt/Rh(100) surface. That is, a streaky LEED pattern appeared at 340 K and it changed to a very sharp p(3xl) pattern at about 400 K by heating in 10 -7 Torr of NO or O2 [8]. However, the p(3xl) surface on these two surfaces showed almost equal reactivity to H2 at room temperature. Taking these facts into account, thick Pt layer (ca. 4 monolayers) deposited on P t ~ l ( 1 0 0 ) surface may be responsible to the slow formation of p(3xl) structure. Therefore, the p(3xl) pattern indicates the formation of a common hybrid Rh-O/P-layer on Pt~a(100), RbdPt(100) and Pt-Rh(100) alloy surfaces. Fig. 2 shows the characteristic behaviour of Pt/Rh(100) surface. The hybrid structure of Rh-O/Pt-layer undergoes decomposition at 1000 K and the LEED pattern changes from the p(3xl) to p(lxl) patem on Pt-Rh(100) alloy as well as on RlgPt(100) and Pt/Rh(100) bimetal surfaces.

233

(lxl)Rh(lO0) Electrochemical Deposition

p(lxl)

c( 2x2 ) Pt/Rh ( I O0) (ept =4)

l

( 1 0 -7 T o r r / 7 8 0 K )

02 60L (room temp.)

p(3 x 1 ) + p4g p(Z• )

Hz 60L (room temp.)

l >900K p(1 xl )Pt/Rh(100).,

02

(>SOOK)

:- p(3x 1 ) + p4g p(2x2)

Figure 2 Schematic discription of the reversible change between p(3xl) and p(lxl) on Pt/Rh(lO0) at room temperature by H2 or 02. We are now capable to control PURh bimetal surfaces as well as Pt-Rh alloy surface by chemical restructuring. Based on these facts, our interest is focussed on the catalysis over the controlled surfaces. Catalytic reaction of NO + H2 ( NO l x10-6 Torr, H2 2x10-6 Torr ) was performed on p(lxl) Pt/Rh(100) and p(3xl) Rh-O/Pt/Rh(100) surfaces. the Pt/Rh(100) surface is self-activated during the catalysis at temperatures higher than ca. 600 K. On the other hand, the p(3xl) hybrid surface having RhO/PURh(100) construction promotes the reaction even at ca. 400 K as shown in Fig. 3 curve (ii), where the p(3xl)Rh-O/Pt/Rh(100) surface was prepared by heating the p ( l x l ) P ~ a ( 1 0 0 ) surface in 02 (10 -7 Torr) at 780 K for 10 min. Curve (iii) is the repeated run after nm (ii). It is noteworthy that the ratio of NH3/N 2 of run i) was 0.233 at 780 K, which was very close to the value of 0.277 on the activated p(3xl) surface given by nm (ii). Therefore, we can conclude that the Pt/Rh(100) surface undergoes self-activation during catalysis by chemical Fig. 3 (i) shows the reaction performed on a p(lxl) surface Pt/Rh(100) having Pt enriched topmost layer by annealing at 1000 K for 5 min. It is clear that the surface is poorly active for the fomaation of N 2 at T < ca. 600 K, but the surface

234 becomes active at temperaure higher than ca. 600 K, which seems to suggest that restructuring, and the catalysis takes place on this hybrid surface of Rh-O/Ptlayer. i

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I

750

Temperature (K) Figure 3 Catalytic reaction of NO (lxlO -6 Torr) + H 2 (2x10-6 Tort) on Pt/Rh(lO0) surfaces with different constructions. (i); p(lxl)Pt/Rh(lO0), (iO; p(3xl)Rh-O/Pt/Rh(lO0), (iiO; repeated run after the run (iO. From the view point of the hybrid surface formation, NO + H 2 reaction on Pt(110) and Rh/Pt(110) surfaces are very interesting, because Pt(110) surface is poorly active compared to Pt(100) surface as shown in Fig. 4, that is, this reaction is a typical structure sensitive reaction. To compare the Rh/Pt(110) surface to Rh/Pt(100), we prepared Rh/Pt(110) surface by depositing Rh ions on a missing row p(lx2) Pt(110) surface. Rh deposited Pt(110) surface did not give any LEED spots because too thick Rh layer was deposited. Rh atoms were removed from

235 the surface by Ar discharge sputtering and heating in 0 2 at 770 K, and the first LEED pattern appeared was c(2x2) it changed to p(lx2) pattern when the thickness oftheRh atoms were lower than one monolayer. The p(lx2) Rh/Pt(110) surface gives very high catalytic activity for the reaction of NO + H2 as shown in Fig. 4. Although the reaction of NO + H2 on Pt(110) and Pt(100) surfaces is

I I I

S

Rh/Pt(11 O) ( 0 - 0.43)

I

I

I I I I I I I I

:3

v

d (0

iiiii

E

Pt(lO0)

!i;

t._.

0 ii

t'M

Z

Pt(110) m ~

200

300

A

6oo ' 7bo 400 500 Temperature (K)

800

Figure 4 TPR of NO + H2 on Pt(110), Pt(100), and Rh/Pt(11 O) surfaces. highly structure sensitive as being Pt(100) >> Pt(110), Rh/~(110) and Rh/Pt(100) surfaces give almost equal catalytic activity. From these results, we can conclude that the Pt-Rh catalyst is self-actived, and a cormnon hybride surface is built up on Pt-Rh(100) alloy as well as on Pt/Rh(100), RldF't(110) bimetallic surfaces during the catalytic reduction of NOx.

236 ACKNOWLEDGEMENT

This work was supported by the Grant-in-Aid for Scientific Research (05403011) of the Ministry of Education, Science and Culture of Japan, and one of the authors (Tamura) acknowledges KAO Corporation for giving a chance to study this work.

REFERENCES

T. Yamada and K. Tanaka, J. Am. Chem. Soc., 113 (1991) 1173 ; H. Hirano, T. Yamada, K. Tanaka, J. Siera, P. Cobden and B.E. Nieuwenhuys, Surf. Sci.,262 (1989) 97 H. Hirano, T. Yamada, K. Tanaka, J. Siera and B.E. Nieuwenhuys, Vacuum 41 (1990) 134 H. Hirano, T. Yamada, K. Tanaka, J. Siera, and B.E. Nieuwenhuys, Surf.Sci., 222 (1989) L804; H. Hirano, T. Yamada, K. Tanaka, J. Siera, and B.E. Nieuwenhuys, Surf. Sci.,226 (1990) 1 I. Matsuo, J. Nakamura, H. Hirano, T. Yamada, K. Tanaka and K. Tamaeu, J. Phys. Chem., 93 (1989)7747; K. Tanaka, Progress of Theoretical Physics, 106 (1991)419; K. Tanaka and T. Yamada, Research on Chemical Intermediates, 15 (1991) 213 T.T. Tsong, D.M. Ren, and M. Ahmad, Phys. Rev. B., 38 (1988) 7428 ; D.M.Ren, and T.T. Tsong, Surf. Sci., 184 (1985) L439. H. Tamura, A. Sasahara, and K. Tanaka. to be published in Surf. Sci.Letters. J. Siera F.C.M.J.M. van Delft, and B.E. Nieuwenhuys Surf. Sci. 264 (1992)435 M. Taniguchi, E. Kuzembaev and K. Tanaka, Surf. Sci., 290 (1993) L711

A. Frennet and J.-M. Bastin (Eds.) Catalysis and Automotive Pollution Control III

Studies in Surface Science and Catalysis, Vol. 96 9 1995 Elsevier Science B.V. All rights reserved.

237

CHANGES IN MICROSTRUCTURE AND CATALYTIC ACTIVITY EFFECTED BY REDOX CYCLING OF RHODIUM UPON CeO2 AND A1203 J. Cunningham, D. Cullinane, F. Farrell, M. A. Morris, A. Datye* and D.Lalakkad*

Chemistry Department, University College, Cork, Ireland *Farris Engineering Center, University of New Mexico, Albequerque, NM 87131-1341, USA ABSTRACT Prior calcination at Tox > 673 resulted in Rhox/CeO2(A) materials having activities for Ro-type o.i.eq. and for R2-type o.i.x, much enhanced relative to that over CeO2 but in which, unlike Rh/AI203, the oxidised Rhodium component could not be detected by HRTEM or XRD. Observations in reducing conditions were likewise consistent with differences in the nature of Rhodium upon/within CeO2 relative to that dispersed on A1203.

INTRODUCTION

Despite the acloaowledged ilnportance of rhodimn as a componem of three way catalytic converters (TWC's), some tmcertahlties remain concenfing changes in its lnicrostructural characteristics and the occurence of various valence states during various stages of TWC operation [1,2]. Controversy also cominues concenfing file question as to whether or not catalysts featuring rhodimn dispersed on ceria are susceptible to inhibition of their activity by "decoration-encapsulation"-type Strong Metal Support hlteraction (SMSI), or alternatively by rhodimn loss fllrough burial as ions or atoms witlfin the oxide support [3,4]. Various experimemal approaches have been adopted ha this study ha efforts to resolve some of these uncertahlties: namely (i) the use of XRD and HRTEM directed at clarification of microstructural changes induced by redox treatmems; (ii) studies by TPR of how ease of rereduction of oxidised rhodimn species depended upon severity of prior oxidation; (iii) utilization of structure-sensitive hydrogenolyses as probe reactions to gain information concerning file SMSI susceptibility of rhodimn hi metallic form when supported on A1203 or CeO~; and (iv) comparisons of the oxygen-hmldling capabilities of file oxidised catalysts using oxygen isotope equilibration and exchange.

238 EXPERIMENTAL Materials In order to minimise possibilities for spurious metal-support effects associated in the literature with use of RhCl3 as precursor of ceria-dispersed rhodium [5], the materials used in the present study were prepared using rhodium(III) acetylacetonate (Aldrich) as precursor. Wet impregnation at 0.5, 2 or 4 wt% onto the surfaces of the oxide powders was achieved from solution in high purity methanol or tetrahydrofuran, after which samples were dried and calcined in 02 for 2 hr at 823 K. Ceria available from Aldrich (CeO2(A), 16 m2m~) or Rhone-Poulenc (CeO2(r.p.),llO m 2 g~), and Al~O3 (Come, 200 m~-g~) were used as supports. Material Characterizations These were made by temperature programmed reduction in 3% H2+97% Argon (TPR), by high resolution electron microscopy (HRTEM) and by powder Xray diffraction (XRD) on aliquots of the materials both in their "as prepared" states and after preoxidations (HTOx) and/or prereductions (HTR). Powder XRD patterns were collected at RT using a Philips MCD diffractometer feattaJng optoelectronic control to ensure precise measurement of Q values. Peak width, positions and areas were evaluated by computer fitthlg of profiles. Particle sizes, where quoted, were calculated using the Scherrer formula. Detailed comparisons were made between patterns for samples after ageings in air at temperatures up to 1423 K and/or after reductions in 3% CO/He up to 573 K. HRTEM was done at the High Temperature Materials Laboratory, Oak Ridge National Laboratory, using a JEOL 4000 EX microscope. Transmission electron microscopy was also done at the University of New Mexico using a JEOL JEM 2000-FX microscope. The samples for TEM were made by simply dipping the holey carbon grid in the powder and shaking the excess off. No solvent was used in any stage of the sample preparation. Elemental analysis was done by energy dispersive spectroscopy (EDS) using a Tracor Northern System. Reactivity Studies Since structure sensitivity in the hydrogenolysis of n-butane over oxidesupported group VIII metals had been reported [6], this was utilised as a suitable catalytic probe reaction with wlaich to compare activities of the catalysts in net reducing conditions. Particular interest attached to the question as to whether prior high temperature reductions (e.g. HTR773 K) would bring about similar strong inhibition of hydrogenolysis activity of Rh/Al203 or Rh/CeO2 after LTR4~. Such reactivity studies were carried out in quartz-tube differential microreactors and samples of the exit gases were analysed by gas chromatographs fitted with appropriate columns and flame ionisation detectors. A reactant-flow composition

239 ratio of He:H2:C4H10 equal to 20:20:1 sccm was used. Between runs the removal of any carbonaceous deposit was effected by flowing (Hz+He) over catalysts to regenerate them. Experiments aimed at comparing the oxygen-handling activity of preoxidised aliquots of the materials, wlfilst ensuring fllat surfaces remained in an oxidised condition throughout (e.g. Rh"+ox/CeO~), were carried out in a recirculatory reactor system under low pressures of an (16Oz+~80~)equimolar mixture.

RESULTS AND DISCUSSION TEM

Photo (a) in fig. 1 shows the low magnification transmission electron micrograph of Rh/AI203 in its precalcined state. The rhodium particles (shown by arrows) have a rounded morphology and are seen tmifol~y all over the catalyst and the average particle size is ))300 A. EDS confirmed a uniform distribution of rhodium in this catalyst. Photo (b) in fig. 1 shows a high magnification picture of the same catalyst. The lattice spacings on the large particle (shown by the arrow) indicate that the rhodium in this catalyst is present in file form of Rh203. Treatment of this catalyst in 1-12reduced the Rh203 to metallic Rh accompanied by a small decrease in particle size, but otherwise the distribution of particle sizes or the morphology of the catalyst was unchanged. Photo (c) of fig. 1 shows a high magnification view of Rh/CeO2 in the oxidised state. In this case too, EDS confmned the presence of rhodium in amounts similar to those seen on Rh/A1203. However, there is a distinct absence of a particulate rhodium phase on tiffs catalyst, both in the oxidized catalyst which is shown, and the same catalyst reduced in 1-12at 473 K. Tiffs agrees with our previous study [7], where it was shown that on a CeO2 support, Pt was difficult to observe in the TEM, at least in the fresh catalyst, but in that case, the Pt particles could be readily seen after several oxidation-reduction cycles. Murrell et al have previously demonstrated the existence of a dispersed oxidised phase of Pt on Pt/CeO~ [8]. It is possible that such a dispersed oxidised phase of Rhodium here formed on or within CeO2 thereby making the oxidised Rhodium component difficult to detect. [9]. XRD 4% Rh/CeO:: No peaks due to rhodium or its compounds were visible after ageing acac-derived samples at 823, 923 and 1023 K. After a 1123 K trealanent however, peaks readily ascribable to Rh203 could be easily detected (plot a, fig. 2). Between 1123 K and 1423 K the peaks sharpened consistent with average particle size having increased from ca. 300 to 650 A. Other noteworthy points to emerge from particle size measurements included: Firstly, that below 1123 K no rhodia-related peaks were detectable, thereby indicath~g sizes below the X R detection limit even

240

'~

.

~"

,~

'

~,~~:1

i ~ ~

'

. . . . i.'~.~!~:!r,-,-,~,-,.~.:,~i,~.~~!i:?f:...;t ~~.,.~ '~.~'-.,~"t:i:~,:'~:~..:'~. -~-~,~:' .._.., ~:['..~."~ , :."-..-.:.. ~ . . 1.~. '-.'." ~ . ~ - - - ~~,~4~.~:~,~:~.....-.:.~:.: . .~. ., . . , ~ . ...

-iOnm

......

....;..... :-.

1

~,."." ,.~-.i;" ... .......

:!i~,~

, ,,~.., b'~.i,i

FIGURE 1" Transmission electron micrographs of precalcmed materials (a) TEM of Rh d A l~9 s; (b) HR TEM of Rh d A le0 3; (c) HR TEM of Rh o,/Ce O e.

241

A

I

F ~ ~

[

{

......

[ . . . . . . . .

20

| ...........

40

!

_

I .........

I

k) '

2

_

"

_ !

60

"

[degs]

1 ....

2S

t. . . . . . . .

!

B

2_ #l

.4

W C

5n

O

I FIGURE 2: Powder X-ray diffractograms of 4% Rh/Ce02 (Part ,4) and 4% Rh/Al20s (Part B) after treatments as follows: Part A: Rh/Ce02 with CeO2features indicated by vertical lines, metallic Rh by O, Rhodia by * and mixed Rhodium-Ceria phase by #: Plot (a) calcined @ 1123K; plot (b) aged @ 1423 K; plot (e) reduced in CO @ 523 K. Part B: Rh/Al20~ with a-Al20s indicated by vertical lines, Rhodia by * and mixed Rhodium-alumina phase by #: plot (d) calcined @ 823 K; only 2Q angles 15~ ~ are displayed since above this the complex y-Al20s (and related structures) is too complex to reveal additional features; (e) full 2Q scan after calcination @ 423 K. Note the change of y-Al20s to ct-Alz03.

242 for this substantial rhodium loading. As may be seen later, whenever metallic Rh was formed from this same loading it could be detected as particles around 50 A. On that basis it appeared that whatever rhodia particles were present atter calcinations below 1123 K must be smaller than 50 ,A,. That conclusion is strongly supported by the above-mentioned HRTEM observations upon Rh/CeO2 (cf. photo _.cof Fig. 1) which gave no evidence for rhodia particles, although ceria (111)lattice planes with spacings of 3.1/k were readily resolved. Secondly, in many experiments it was found that sizes calculated from different reflections spanned a wide range e.g. after calcination at the highest temperature (1423 K) results ranged 650+50 A, whereas after 1123 K calcination the calculated sizes ranged 200-700 A (average 300 A). These results may be rationalised if rhodia particles were polyerystalline assemblies of individual erystallites having morphologies not corresponding to hemispherical. It has been suggested for Rh/AI203 that raft-like particles may be formed [10] and present XRD results for rhodia upon ceria may not be inconsistent with this possibility in respect of individual mieroerystallites. After ageing at 1423 K new peaks are seen in the diffraetogram not attributable to either ceria or rhodia (plot b, fig. 2). Peaks due to Rh metal presumably formed via the high temperature loss of oxygen - are indicated on the plot 2b. This agrees with recent work on rhodia by Carol and Mann [11]. However, other new peaks (also indicated) point to the formation of a completely new phase which has not yet been identified, but might be the Rhodium analogue of a surface-related, mixed phase such as reported previously for Pt upon CeOz [12]. When the 1423 K aged sample was reduced in CO at 523 K and re-oxidized at 573 K complete removal of peaks due to the mixed phase was achieved (but not of peaks due to metal, which rather hacreased in size during the reduction process cf. plot c fig. 2). However, the metallic particles produced by this 523 K reduction with CO appeared resistant to reoxidation at 573 K (cf. TPR data below). XRD 4% Rh/y-Al~O3: After agehlg at 823 K peaks due to y-A1203 were observed together with others attributable to the presence of rhodia (plot d, fig. 2). As a result of ageing at temperatures between 823 K and 1423 K rhodia particle size increased from c_aa.50 (+30) to c~. 400 (• A. Lack of consistency between particle-size calculated from different reflections was evident, consistent with observed rhodia particles being polycrystalline assemblies within which individual crystallites may not be equiaxed. The contrast between this facile detection of rhodia upon A1203 and its non-observance upon the ceria-supported sample indicates that one effect of the ceria was to produce/maintain oxidised Rhoditun ha hyper-dispersed form at temperatures up to 1023 K. However, after calcination at 1123 K the size of the rhodia particles on alumina was about 120+50 A which was smaller than observed for Rh/CeO2 similady-pretreated. After ageing at 1423 K dramatic changes in the pattern occurred with the appearance of new peaks due to metallic Rh, as well as others due to an

243 unidentified phase, and yet others attributable to a-alumina and rhodia (plot e, fig. 2). Yates et al [13] have suggested that during the high temperature processing of Rh/AI203 there is not only some solution of the rhodium oxide to give a surface mixed phase but also an encapsulation ofrhodia particles as the 3' ~ ot alumina phase transformation occurs. In our work the collapse at the g-structure was observed atter ageing at 1400 K, thereby lending support to this hypothesis. However, it should be pointed out that the formation of the mixed phase is not dependent upon support structure collapse, since heating a physical mixture of Rh203 and ~x-A1203at 1223 K in air for 2h rapidly produces the mixed-component phase. Redox Cycles (TPR-T,o,)

Comparisons between the TPR profiles at 10 K min~ from aliquots of rhodium-loaded and rhodium-free CeO2 and A1203 supports in their 'as prepared' condition (i.e. after calchaation at 823 K) demonstrated that a reduction feature onsetting at ca. 330 K and exhibiting a maximum at 390 K originated from the rhodia component. Following that initial (and subsequent) TPR runs up to TR-873 K, aliquots were retained in-situ whilst being cooled to 295 K in 3% Hz/Ar, after which they were exposed to a flow of pure, pre-dried 02 for 2h at a reoxidation temperature, T~, before being cooled to 295 K in Oz, flushed with 3% Hz/Ar and another TPR run made in standard conditions. Repetition of that sequence at progressively higher Try0, yielded, for each of the daodium-loaded materials, a set of TPR profiles from which the following features emerged concerning the extent to which 2h at various T~ restored the H2-reduced rhodium component to oxidised form(s) reducible in the range 350-430 K: (i) no such reoxidation was detectable after T,ox@ 373 K, whereas 18%, 46% and 100% of flint ultimately attahmble was achieved by T~x @ 473, 573 and 673 K respectively; (ii) wlfilst position of T~x of the main TPR feature shitted progressively from 350 K after T~ox@ 473 to 430 K after Tro~@ 1073 K, continued existence of a lower-temperature shoulder at ca. 373 K (which became clearly resolved atter T~ox@ 1073 K) suggested the continued co-existence of a minor, more easily reduced form of rhodia (possibly surface or near surface) together with the major and more diffictdt to reduce fonn (possibly wiflain bulk) achieved by Tr~ ---773 K. A set of such profiles similarly compiled for 4% Rh/AI203 again appeared consistent with two distinguishable fonns of dlodium alter Trox -> 973 K. However in that material the more easily reducible fonn ( T ~ ~ 373 K) was the major component after Tro~< 873 K - an observation which may be correlated with the TEM and XRD results above demonstrating the existance of sizeable rhodia particles upon that material after ageing at such temperatures. Another point made clear by the sets of TPR profiles for Rh/CeO, and Rh/A1203 is flint, irrespective of T~oxvalues within the

244 range 673 ~ 1023 K, subsequent exposure to H2 at TR >__450 K sufficed for rapid conversion of the rhodium content to its reduced form:

Oxygen-handling Properties of Preoxidised Materials Advantages in the use of an equimolar, isotopicaUy non-equilibrated (i.n.eq) mixture of 1602 ~-- 1802 to probe the oxygen-handling properties of oxidic materials include capabilities to detect: (a) activity of the surfaces at 295 K for Ro-type homophase isotopic equilibration (o.i.eq) as per eqn (0), via the intermediaey of very weakly held four-oxygen-atom surface species [14]; and (b) activity at higher temperatures for thermally activated heterophase oxygen isotope exchange (o.i.x) of types Rt and R2 as per eqns. 1 and 2, possibly via the intermediacy of strongly bonded O- and O ~species respectively [15]. Ro-type

P('SO,)o.5+ p(1602)0.5 ~ P('60'sO)0.5 + P('602)o.z5 + P('sO00.2,

Eq. (0)

R,-type

'sOz(g) "[- 1602-(S) ~

160"O(g) + 'sO2(s)

Eq. (1)

R2-type

1802(g) + 21602"(S) ~

1602(g) "~- 21802"(S)

Eq. (2)

The tL,-process was promoted at 295 K by preoxidised samples of ex Rh.ac.ac. Rhox/CeO2(A) samples, but not by the rhodium-free supports nor by ex-RhCl3 materials. Thermal activation was necessary to bring about o.i.x., as evidenced by onset of variations in partial pressures of ~802, ~602 and ~60~sO during upward ramping of reactor temperature. Over rhodium-free CeO2, no tL,-type o.i.eq. occurred, with the result that when o.i.x, did onset at ca. 773 K it operated on the i.n.eq, mixture and resulted hi increases m/z = 32, equivalent decreases at rn/z = 36, but with very little increase at m/z = 34. Those changes are consistent with operation of an R2 or place-exchange mechanisms involving vacancy-pair creation and removal. Figure 3 illustrates the thermally activated changes hi isotopic composition of the gas phase over Rhox/CeO2 and demonstrates onset of o.i.x, at ca. 523 K, i.e. ca. 250 ~ below that over CeO2 alone. Since the Rh/CeO:(A) material already exhibited Ro-type activity at 295 K, operation of o.i.eq, had effeeted a change to the isotopically equilibrated composition as per eqn. O during the period of hlcrease from 295 to 523 K. Slopes of the relative rates of change away from that composition, evident in fig. 3 as a result of the onset of o.i.x, at 523 K, are consistent with operation of a mainly R2-type o.i.x, process. This observation that oxidised species within or upon RhJCeO2 made such o.i.x, possible at much lower temperature than for Rhodia-free Ceria is qualitatively very similar to reports of o.i.x, promotion over Sr2§ relative to La203 [16], and a similar

245 interpretation seems appropriate, viz. in terms of a promoting effect of an enhanced concentration of oxygen vacancies caused by incorporation of lower valent cationic dopants.

~OOO i

! 'ralO

o

lm

a~

T

ma ~

4m C*Q

~

~

70o

FIGURE 3: TPOIX profiles of additional changes m isotopic composition of an o.i.eq, dioxygen mixture over RhJCe02 upon ramping temperature at lO~mm ~.

Hydrogenolysis of n-butane Linear ArrhelfiUS plots were obtained for temperature dependence of steadystate activities of 'fresh' samples of Rh/CeOz and Rh/A1203 in n-butane hydrogenolysis at T~ 423-473 K. These plots indicated closely similar activation energies of 38 and 39 kcal molL respectively, but showed hydrogenolysis rates over RldAlzO3 to be uniformly nine times larger than over Rh/CeO2 at equal T_. Results showing the extent to which Rh/CeO2 hydrogenolysis activity, and the selectivity towards ethane, could be modified by subsequem oxidation reduction cycles at lfigher temperatures arc smnmarised in Table 1. Chmlges in activity arc normalised relative to that observed for the fresh aliquot at the same T~, and data in the Table make clear that whereas oxidation-reduction cycles caused significant reversible chmlges in the

246 ethane selectivity of Rh/AI203, the ethane selectivity of Rh/CeO2 was little affected by such cycles. The reported values for ethane selectivity were recorded under temperatures where the methane/propane product ratio was approximately 1.3, and did not change with catalyst pretreatment. The C~-C3 ratio near unity indicates that hydrogenolysis of the n-C4 involves cleavage of a single C-C bond during the turnover of a n-C4 molecule. Differences in the product distribution can then be related to cleavage of the n-C4, at the central bond versus the terminal bond scission. On Rh/A1203, it is seen that the mole fraction of ethane in the product drops from ~ 0.5 in the flesh state to >>0.18 due to oxidation and this drop is reversed by high temperature reduction whereas no such changes occurred for Rh/CeO2.

Table 1: Selectivity

Effects of HTO~ and HTR upon n-butane Hydrogeneolysis Activity and

Pretreatment Sequence

Nonrmlized Activities Rh/AI203 Rh/CeOz

Ethane Selectivity Rh/AlzO3 Rh/CeO2

1. Fresh (LTR673K)

1.00

1.00

0.484

0.401

2.1st HTOx rnK

0.69

1.82

0.218

0.488

3.1st HTR 773K

0.075

0.058

0.398

0.488

4.2nd HTOx773K

0.78

1.75

0.184

0.441

Those contrasting observations may be understood within the context of observations and interpretations developed in previous studies of relationships between ethane selectivity and dlodium particle size upon A1203 and SiO2 supports [6]. On low weight loading Rh catalysts, where the particles were so highly dispersed that they were invisible by the TEM, oxidation-reduction cycles did not cause any change in either the activity or the ethane selectivity. On higher weight loading catalysts where the rhodium was present as well defined particles, the oxidationreduction cycles caused significant changes in the activity and ethane selectivity that resembled those on macroscopic single crystals [8]. In flaat work it was argued that by virtue of their size, the surface smlcture of the small particles (< 10/~) could not be altered because of hlsufficient room to pack the atoms in different ways. In the present study, the Rh/AI203 with particle size of >>30 nm showed reversible changes in ethane selectivity during n-butane hydrogenolysis, while the Rh/CeO2 catalysts

247 with no detectable particulate Rh phase exhibited no such cycling. This would be consistent with the rhodium particles on the CeO2 support being very highly dispersed and/or having fonr~ed a complex that 'locks' them in a state where they did not undergo significant morphological changes under the pretreatments used in the hydrogenolysis studies.

ACKNOWLEDGEMENTS

Financial support for the research at UCC came in part from Contract SC1-CT910704 with DGXII of The European Commission: that for work performed at The University of New Mexico was provided by The Petroleum Research Fund of The American Chemical Society. High resolution TEM was performed at the High Temperature Materials Laboratory, a user facility supported by the U.S. Department of Energy at Oak Ridge National Laboratory, with additional work being performed at the Electron Microscope Laboratory witlfin the Department of Geology, University of New Mexico.

248 REFERENCES

9

10 11 12 13 14 15 16

L.D. Schmidt and K.R. Krause, Catalysis Today, 12 (1992),264. C.Z. Wan and J.C. Dettling, CAPoCI (eds. A. Crucq and A. Frennet,P359) (a) J. Cunningham, S. O'Brien, J. Sanz, J.M. Rojo, and J.L.G. Fierro, J.Mol.Catal.,57, (1990), 379. (b) J. Cunningham, D. Cullinane, J. Sanz, J.M. Rojo, J.A. Sofia, and J.L.G. Fierro, J.Chem.Soc.Farad.Trans., 88, (1992), 3233. (a) S. Bemal, F.J. Botana, J.J. Calvino, M.A.Cauqui,G.A.Cifredo, A. Jobacho, J.M. Pintaro and J.M. Rodriquez-Izquierdo,J.Phys.Chem.,97 (1993) 4118. (b) J.E1.Fallah, S. Boujmm, H. Dexpert, A. Kiennemann, J. Majerus, O. Touret, F. Villain and F. Le Nonnand, J.Phys.Chem., 98 (1994), 5522. H. Abderrahim and D. Duprez, Proc.9fll Intem.Cong.Catal. (eds. M.J. Phillips & M. Teman) Vol. 3, p.1296. D.S. Kalakkad, S.L. Anderson, A.D. Logan, E.J. Braunschweig, J. Pena, C.H.F. Peden and A.K. Datye, J.Phys.Chem. 97,(1993), 1437. D.S. Kaladdad, A.K. Datye and H.J. Robota, Appl.Catal.B., 1, (1992), 191. L.L. Murrell, S.J. Tauster and D.R. Anderson, 1Oth North American Catalysis Lexington, KY (1991). H.C. Yao, H.K. Stephen and H.J. Gandhi,J.Catal.,61(1980),547. D.J.C. Yates, and E.B. Prostridge, J.Catal., 106 (1987), 549. L.A. Carol and G.S. Mann, Oxid.Metals, 34 (1990) 1. T.M. Bollinger and J.T. Yates, J.Phys.Chem., 95 (1991),1694. J.G. Chen, M.L. Collainni, P. Chen, J.T. Yates and G. Fisher, J.Phys.Chem., 94 (1990), 5059. J. Cunningham in "Stwface and Near-Surface Chemistry of Oxide Materials" (eds. J. Nowotny and L-C. Dufour) Materials Science Monograph 47, Elsevier, Amsterdam, 1988, P.345. (a) J. Novakova, Catal.Rev., 4, (1970), 77; (b) E.R.S. Winter, J.Chem.Soc., (1968), 2889. Z. Kalenik and E.E. Wolf (a) Catal.Lett. 11(1991), 309, and (b) Catalysis Today, 13 (1991),255.

A. Frermet and J.-M. Bastin (Eds.) Catalysis and Automotive Pollution Control I11 Studies in Surface Science and Catalysis, Vol. 96 9 1995 Elsevier Science B.V. All rights reserved.

249

CATALYTIC OXIDATION OF PROPANE OVER P A L L A D I U M SUPPORTED ON ALUMINA AEROGEL. EFFECTS OF THE P R E T R E A T M E N T ON THE ACTIVITY AND INVESTIGATION OF THE STATE OF P A L L A D I U M BY GRAZING-INCIDENCE-X-RAY DIFFRACTION C. Hoang-Vana, R. Harivololonaa and S. Fayeulleb aURA au CNRS "Photocatalyse, Catalyse et Environnement", Ecole Centrale de Lyon, B.P. 163, 69131 Ecully COdex, France. b URA au CNRS "Laboratoire Mat6riaux-M6canique Physique", Ecole Centrale de Lyon, B.P. 163, 69131 Ecully C6dex, France.

ABSTRACT

The effects of the pretreatment conditions on the activity in propane oxidation of Pd and Pt supported on A1203 aerogel catalysts and on their structure have been investigated by temperature-programmed oxidation and GIXD analysis. The results suggested that both PdO and Pd ~ were active sites for Pd catalysts. It was found that PdO generated under an oxidizing reaction mixture was particularly active for initially reduced samples, whereas for aged catalysts the dense faces on large crystallites were likely the active phase. In contrast, the active sites on Pt catalysts very likely consisted of Pt ~ Furthermore, a large decrease in activity for aged catalysts tended to show that Pt was considerably less resistant to sintering in oxidizing environments than Pd. Under an oxidizing reaction mixture, the half conversion temperature for a Pd/A1203 -aerogel was slightly lower than those observed for both a Pt/Al203-aerogel and a Pt-Rh/AI203 catalyst.

1. INTRODUCTION

Palladium catalysts have long been recognized as having desirable performance properties in automotive emission control. In addition to its ready availability and low cost relative to platinum and rhodium, palladium is superior to platinum for CO oxidation and oxidation of unsaturated hydrocarbons [1].

250 However, improvements need to be made, particularly in the Pd-catalyzed conversion of both NOx and saturated hydrocarbons, if Pd-only three-way catalysts are to be developed. In a previous study, we found that Pd (lwt%) catalysts supported on finely divided alumina aerogels were more active, in the oxidation of CO by NO and 02, than both Pd and Pt-Rh supported on commercial aluminas [2]. More recently, a study of propane oxidation over Pd supported on alumina-based aerogel catalysts led to the conclusion that favorable ensembles of active sites contituted by pdo atoms and pdn+ ions might exist for this reaction [3]. The present work is concerned with the influence of the pretreatment of an alumina-aerogel supported Pd catalyst on its activity in propane oxidation. The state of Pd and the crystalline state of alumina aerogel were investigated by grazing-incidence X-ray diffraction (GIXD). To our knowledge, this method is applied for the first time to supported metal catalysts. In addition, a comparison of the structural and catalytic oxidation properties of Pd, Pt and Pt-Rh supported on alumina carriers was made.

2. EXPERIMENTAL

2.1. Catalysts The alumina aerogel (490 m2.g-1, 1.3 cm3.g-1 micro-mesopore volume) was prepared from aluminum see - butoxide dissolved in see - butanol by hydrolysis with a stoichiometric amount of water. The alcogel was then dried in an autoclave under supercritical conditions with respect to sec - butanol [4]. Two conventional alumina xerogels ( Degussa : 110 m2.g-1 and R.P. : 100 m2.g-1 ) were also used as supports of Pd and Pt-Rh catalysts. Pd and Pt catalysts were obtained by impregnation of the supports with methanolic solutions of palladium or platinum acetylacetonates. The solids were then dried at 383 K for about 15 h. The Pt-Rh/AI203 three-way catalyst was prepared by impregnation of the support with a solution of H2 PtCI6 and RhC13 followed by a drying in air at 673 K [5]. 2.2. Textural characterization Surface area measurements and precious metal dispersion determinations by CO chemisorption were reported previously [2]. The chemical composition of the catalysts and their textural characteristics are given in Table 1. Prior to the BET or CO chemisorption measurements, the samples were either reduced by H2 at

251 773 K for 3h (fresh catalysts) or first treated at 1273 K in flowing 02 containing 10% of water vapour for 4h and then reduced in H2 at 773 K (aged catalysts).

Table 1 Chemical composition and textural characteristics of catalysts Catalyst

Surface area (m2.g-l) Metal dispersion (%) Fresh catalyst Aged catalyst Fresh catalyst Aged catalyst Pd/AlzO3-A a) 280 134 22 d) 17 e) Pd/AIzO3-D a)

110

97

Pt/A1203 -A a)

325

159

25 d)

7.5

52

11

Pt-Rh/AI203 b)

1O0 -c) 55 _ c) a) Metal loading : ~1 w t % - A : aerogel - D : Degussa (gamma structure) b) Conventional dechlorinated three - way catalyst : 1% Pt - 0.2% Rh/A120315]. c) - : not measured d) Pd particles diameters in the range 3-9 nm as observed by TEM e) Pd particles in the range 16 - 80 lira as observed by TEM. A few big alumina particles (0.8-7 mm) contained up to 5 wt % Pd as revealed by STEM analysis. 2.3. Pretreatment conditions Before GIXD examinations or activity measurements, the catalyst samples were submitted to a treatment under different conditions that are summarized in Table 2.

Table 2 Conditions of catalyst pretreatments Pretreatment

Atmosphere

reduction calcination activation under reactants

hydrogen air 3000 ppm C3H8 + 1.5% 02 in N2 ( s - 1) 02 + 10%H20

aging

Temperature (K)

Duration (h)

773 773 773

3 3 3

1273

4

252

2.4. GIXD analysis The grazing incidence X-ray diffraction (GIXD) measurements were performed using a 2-circle vertical goniometer which was specially designed in the laboratory. Scheme of the apparatus is shown on figure 1. Copper radiation was used without monochromator. A lithium-doped silicon cristal was used as the detector (operating at liquid nitrogen temperature) and the CuKa radiation (1 = 0.154 nm) was selected owing to a multichannel analyser. Soller slits were installed on the incident beam to get a parallel beam and on the diffracted beam to limit the instrumental width of Bragg peaks to about 0.15 ~ (theta) measured on silicon reference sample. The zero incident angle between the surface of the sample and the incident X-ray beam was carefully determined by measuring the intensity of fluorescence on a pure iron sample (for which the critical angle of total reflection is equal to 0.38~ The exact position was then defined by using a laser beam reflection. Powder samples were deposited on glass slides and carefully flattened to obtain as smooth as possible surfaces. The incident angle was usually ranged between 0.5 and 2 ~ The penetration depth calculated owing to Fresnel formula [6] was equal to 1.5 mm in pure alumina for an incident angle of 1~ X-ray spectra were recorded for 2q varying from 20 to 80 ~ at a constant speed of 0.02~

SAMPLE

O~

SLIT $2

SLIT S 1

SOLLER SLITS S01

2O SOLLER SLITS S02

DETECTOR (SiLl)

Soller Slit S01 =0.4 x 60 mm Soller Slit S02 -0.1 x 60 mm Slit $1 = 0.5 mm Slit $2 = 2 mm

Figure 1. Scheme of the GIXD experimental set-up

X-RAY SOURCE

253

2.5. Activity measurements Propane oxidation was studied by using a flow reactor system equipped with a flame ionization detector (FID). The reactant mixture was composed of 3000 ppm C3H8 in N2 with varying amounts of oxygen and the total flow rate was kept constant at 20 L.h -1. The catalyst weight was 0.05 g diluted with 0.15 g of inactive ct-ml203. The pretreatment was carried out under various conditions (see Table 2). The conversion of propane was measured at increasing temperatm'es (1.4 K.min -1) in the range 423 - 773 K. The stoichiometry of the feedstream was characterized by the ratio s = (02)/5 (C3H8) (stoichiometric mixture for s = 1 and oxidizing mixture for s>l).


3.1.GIXD results Figure 2 shows the GIXD spectra of Pd/A1203-A catalyst previously reduced (sp. A), calcined (sp. B), aged (sp. C) or reduced after aging (sp. D). The conditions of these pretreatments are indicated in Table 2. Alumina aerogel support was poorly crystallized in the kappa form after reduction or calcination at 773 K (sp. A and B) whereas Pd ~ or PdO were distinctly detected after reduction (sp. A) or calcination (sp. B), respectively. After aging, PdO and 8-A1203 were observed (sp. C) and a subsequent reduction revealed Pd ~ and 8-A1203 (sp. D). GIXD spectra (not shown here) were also recorded for initially reduced or calcined samples after the catalytic test under a stoichiometric or an oxidizing reaction mixtures (s = 1 or s = 4). In all cases, ~:-A1203 was transformed into ot-A1203. For the reduced sample, Pd ~ remained unchanged for the s = 1 mixture but was completely oxidized into PdO under the s = 4 mixture. The initial PdO phase in the calcined smnple was partly reduced into Pd ~ (Table 3). GIXD spectra concerning the Pt/AI203-A catalyst are shown in Figure 3. Distinct differences were observed between Pt/A1203-A and Pd/A1203- A catalysts : i) y-AI203 was detected for the calcined catalyst (sp. A) instead of the kappa form for Pd/AI203 - A ; ii) PtO2 and Pt ~ were present in the calcined sample (sp. A) but this oxide was completely reduced after a test under the stoichiometric mixtm'e (sp. B) and iii) after aging, only Pt ~ was detected on the 8A1203 support (sp. C). These differences may stem from the differences in the

254

12= Pd

PdO

3 = ' k a p p a AI 4 = delta AI

2 203 1

4 4

4

1

44

4

,

4 4

4

C ---,w

-~- . . . .

I~

20

2

3

,~

30

3

2 3

40 2 THETA (~

50

60

F i g u r e 2. G I X D s p e c t r a o f P d / A l 2 0 3 - A afier " A 9r e d u c t i o n - B 9calcination C: a g i n g - D 9a g i n g + r e d u c t i o n (see Table 2 f o r c o n d i t i o n s ) I

20

[

1 = Pt

3 = gamma

2 = PtO2

4 = delta AI203

I

30

I

AI2Oa

1

1

I

40 2 THETA (~ F i g u r e 3. G I X D s p e c t r a o f P t / A l 2 0 3 - ,4 a f t e r " A

!

50

60

9c a l c i n a t i o n - B 9c a l c i n a t i o n

+ reaction (s= 1) - C 9a g i n g (see Table 2 f o r c o n d i t i o n s )

255 dispersions of Pt and Pd on the alumina support (Table 1) and in the intrinsic properties of these two noble metals. A higher dispersion of Pt (52% vs 22% for Pd) may enhance the metal-support interaction and leads to a deeper structural transformation of the A1203 aerogel cartier after the calcination treatment. On the other hand, Pt has a higher ionization potential (8.9 vs 8.3 eV for Pd) and its oxide has a lower stability. PtO2 is known to be unstable at 973 K even under an oxidizing atmosphere [7]. Therefore, only Pt ~ was detected after a test under the stoichiometric mixture or after the aging treatment. GIXD results are summarized in Table 3 which also indicates the phases detected for an aged Pd/AI203 - D (PdO and d-A1203) and an aged three-way Pt-Rh/A1203 catalyst (Pt ~ and d-A1203).

Table 3 Structure of Al203 support and state of deposited metal by GIXD analysis catalyst a)

Pd/A1203 - A

Pd/A1203 - D Pt/A1203 - A Pt-Rh/A1203 a) see Table 1

pretreatment b) reduction calcination aging aging + reduction reduction + reaction (s=l) reduction + reaction (s=4) calcination + reaction (s=l) aging calcination aging calcination + reaction ( s - l ) aging b) see Table 2

A1203 kappa kappa delta delta gamma gamma gamma delta gamma delta gamma delta

metal phase Pd ~ PdO PdO Pd ~ Pd ~ PdO PdO + Pd ~ PdO Pt ~ + PrO2 Pt ~ Pt ~ Pt ~

3.2. Propane oxidation 3.2.1. Pd/AI203 - A The light-off curves of Pd/Al203 - A in the oxidation of propane under a stoichiometric reaction mixture are shown in Figure 4 A. Prior to the catalytic test, the catalyst was treated in situ at 773 K under different conditions (see Table 2). At conversions between 30 and 70%, the calcined sample showed the highest activity and the reduced one, the lowest. The curves of Figure 4 B concern an aged Pd/Al203 - A sample whose activity was almost the same as that of a reduced sample (lower curves) whereas an

256 aging-reducing combined pretreatment led to a distinctly higher activity (upper curve).

Figure 4 C illustrates the effect of oxygen concentration on the activity of prereduced Pd/AI203 - A samples. For reaction mixtures s = 1, s = 1.5, s = 2, s = 4 and s = 6, the concentration of propane was maintained at 3000 ppm, while that of oxygen was 1.5, 2.25, 3.0, 6.0 and 9.0%, respectively (N2 diluent). The highest activity was observed for s = 4, which showed that a large excess of 02 was beneficial to the activity of the reduced catalyst, but that a too large excess (s = 6) was detrimental.

3.2.2. Pt/AI203- A The effects of pretreatment and oxygen concentration in the reaction mixture on the activity of a P t / A l 2 0 3 - A catalyst are illustrated by the curves of Figure 5. In contrast with Pd/Al203 - A, the activity of Pt/A1203 - A was much lower under an oxidizing mixture (s = 4) than under a stoichiometric one (s = 1) for both samples, either reduced or aged and then reduced prior to the catalytic test. Table 4 summarizes the results obtained in propane oxidation. The light-off temperature, T50, (at 50% of C3H8 conversion), considered as representative of the catalyst activities, are given for a stoichiometric (s = 1) and an oxidizing (s = 4) mixtures (last columns). For comparison purposes, results obtained for a Pd/A1203 - D and a Pt-Rh/A1203 catalysts are also reported in this Table. The results showed that A1203 aerogel was a better support for palladium than the conventional A1203 - Degussa and, for the stoichiometric reaction mixture, Pt/Al203 - A was more active in propane oxidation than Pt-Rh/A1203 and Pd/A1203 - A. However, under an oxidizing mixture (s = 4), Pd/A1203 - A was slithtly more active than the other catalysts tested (Table 4, last column).

3.3. Correlation structure-activity A tentative correlation between the structure and the activity of the studied catalysts can be made by comparing the results in Table 3 with those in Table 4. For the Pd/AI203 - A catalyst, the light-off temperature (T50) was decreased by 53 K when the originally reduced sample was tested under the oxidizing mixture (s = 4) instead of the stoichiometric one (s = 1) (Table 4). Therefore, PdO that was generated under the oxidizing mixture constituted very active sites, in comparison with Pd ~ still detected under the stoichiometric mixture (Table 3). This conclusion is in agreement with the work reported by Hicks et al. [8] which showed that the oxidation of an originally reduced Pd/A1203 catalyst formed new active sites associated with an increase in the rate of methane oxidation. On the other hand, after the aging treatment followed by a reduction prior to the catalytic

B Fig. 4.8

.

O

reduction saint a[ing+reduction

550

600

650

700

7 50

550

600

reaction temperature (K)

650

700

750


LOO

600

650

700


750

450

500

550

600

650

700

750


Figure 4. Pvopne oxidation over PaYAl.03 -A - (A). E m ofpretivatments @oichiometric reaction mixture) - @). E m of agng (itoichiometnicreacton mixture) - (C). Efects of 0 2 concentration in the reaction mixture mhcedsamples. Figure 5. Propme aridation over Pt/AlO3-A. E m s ofpretmmnentsd o 2concentmtion in the reaction mixture.

258

Table 4 Effect of catalyst pretreatment on the light-off temperature (at 50% conversion : 7'50)for propane oxidation under stoichiometric (s=l) or oxidizing (s=4) reaction mixtures. catalyst a) pretreatment b) Tso(I() Tso(I() stoichiometric oxidizing mixture (s=l) mixture (s=4) reduction 633 580 Pd/A1203 - A calcination 603 610 activation under reactants 607 _ c) aging 635 _ c) aging + reduction 611 609 Pd/A1203 - D reduction 676 589 aging + reduction 611 616 reduction 513 587 calcination 513 608 activation under reactants 513 _ c) Pt/A1203 - A aging + reduction 539 624 reduction 571 589 Pt-Rh/A1203 aging + reduction a) see Table 1

b) see Table 2

565

_ c)

c) Not measured

test under a stoichiometric mixture, the temperature of half conversion was lower by 22 K than that observed for the only reduced sample (611 vs 633 K, Table 4), although sintering of a number of Pd particles occurred during the aging treatment (Pd particles of 16-80 nm were observed by TEM). This is in favour of the hypothesis that the reaction occurs on highly active dense faces present on large Pd crystallites [9]. After the catalytic test, "/-A1203 was always detected for samples pretreated at 773 K. The aging treatment led to the formation of 5-A1203 9Baldwin et al. [10] found that Pd supported on 5-A1203 was much more active than its homologue supported on y-A1203 in methane oxidation. The authors attributed that difference in activity to a difference in the morphology of palladium on various supports [10]. Similar support effect can also be advanced for Pd/AI203-A catalysts pretreated under different conditions. For the PtA1203 - A catalyst, lower activities were always observed for the test under an oxidizing atmosphere (Table 4, compare the last two columns). Therefore, the active sites of this catalyst consisted of Pt ~ and even a partial (or superficial) oxidation of platinum led to a decrease in its activity. Furthermore, an

259 aging followed by a reduction prior to the catalytic test distinctly lowered its activity, in contrast with what oceured with the Pd/A1203 - A catalyst. These results are in agreement with the much higher resistance to sintering of Pd, as compared with Pt, in oxidizing environments (see Table 1 and ref. [11 ]).

REFERENCES

1

W.B. Williamson, J.C. Summers and J.A. Scaparo, in R.G. Silver, J.E. Sawyer and J.C. Summers (eds.), Catalytic Control of Air Pollution : Mobile and Stationary Sources, ACS Symp. Ser. N ~ 495, 1992, p. 26. C. Hoang-Van, B. Pommier, R. Harivololona and P. Pichat, J. Non-Cryst. Solids, 145 (1992) 250. C. Hoang-Van, R. Harivololona and P. Pichat, Europacat. 1, Montpellier, Sept. 1993. S.J. Teichner, in J. Frick (ed.), Proc. 1st Int. Symp. on Aerogels, Springer Proceedings in Physics, vol.6, 1986, p. 22. J.L. Duplan, thesis N ~ 91-91, University of Lyon (1991 ). M. Brunel, F. de Bergevin, Acta Cryst., A 42 (1986) 299. T. Huizinga, I. Van Grondelle and R. Prins, Appl. Catal., 10 (1984) 199. R.F. Hicks, H. Qi, M.L. Young and R.G. Lee, J. Catal., 122 (1990) 295. P. Briot and M. Primet, Appl. Catal., 68 (1991) 301. 10 T.R. Baldwin and R. Burch, Appl. Catal., 66 (1990) 337. 11 J.C. Summers and D.R. Monroe, Ind. Eng. Chem. Prod. Res. Dev., 20 (1981) 23.


A. Frennet and J.-M. Bastin (Eds.) Catalysis and Automotive Pollution Control IH


261

CHARACTERIZATION OF SURFACE AND BULK OXYGEN SPECIES OF THREE WAY CATALYSTS BY 02 TPD AND H2 TPR. C. Boulya, K. Chandesb, D. Mareta and D. B ianchib aE. C.I.A, R&D Center, 25550 Bavans, France. bL.A.C.E, Universitd Claude Bernard Lyon I, ISM, 43 bd du 11 Novembre 1918, 69622 Villeurbanne, France ABSTRACT The deactivation of three way catalysts (TWC) can be studied by the determination of the change of some of their properties such as: specific surface area, catalytic activity or precious metal dispersion. Two qualitative and quantitative methods have been investigated in order to characterize TWC oxygen species: Temperature Programmed Desorption (0 2 TPD) and Temperature Programmed Reduction in hydrogen (H 2 TPR). TPD experiments performed after oxygen adsorption at 873 K, showed four surface oxygen species. Three of them are related to the washcoat (CeO 2, A1203) and the last one to the precious metals (PM): Pt, Rh. Two mains reduction processes are detected by H 2 TPR. The first one, at low temperature, shows two overlapped peaks of hydrogen consumption, respectively assigned to the reduction of metal oxides (T = 251 ~ and to active dispersed CeO 2 in interaction with precious metals (T = 314~ The second reduction process is related to bulk CeO 2 reduction and leads to a consumption of H 2 at temperatures higher than 400~ The evolution of the amounts of oxygen desorbed and of hydrogen consumed during the two temperature programmed experiments, are examined as a function of various thermal treatments of the catalysts.

1. INTRODUCTION

Increasingly stringent vehicle emissions standards make exhaust system (especially catalytic converter) operating conditions more and more severe. Most of the solutions studied to achieve such standards, at lowest cost, are focused on a faster light-off. This can be partially obtained by reducing the distance between the engine and the catalytic converter (close coupled catalyst) and by decreasing heat losses between these two parts. However, these solutions lead to higher

262 operating temperatures which must be taken into account to find out the best trade-off regarding with more stringent durability requirements. This means that parameters causing catalyst deactivation (high temperatures, chemical composition of the gaseous mixtures,...) even if low, must be known very accurately. This knowledge will allow the use of fast development tools leading to catalysts aged exactly in the same way as on the vehicle. Therefore, it will be possible to judge the effect of the whole systems' design to meet the durability requirements and to achieve the best technical and economical compromise. Information on the main parameters controlling the deactivation can be provided by the study of the change of various chemical and physical properties of the TWC such as: BET surface area, chemisorption of probe molecules and catalytic activity. In this paper, another way of catalyst characterization is presented: the analysis of catalyst oxygen species, which are likely to be involved in the catalytic process. It is indeed well known that the addition of promoters and stabilizers (as CeO2) leads to an increase of the resistance to sintering of precious metals [1,2] and to the appearance of new chemical properties (in particular on the oxygen storage) [3-6]. Furthermore, some solutions to meet the requirements of OBDII are based on these oxygen storage properties. A synergy between the two PM is also considered on the CeO2/Al20 3 solids [7]. Two methods of characterization of the various oxygen species have been investigated: Temperature Programmed Desorption (0 2 TPD) and Temperature Programmed Reduction (H2 TPR) Finally, a comparison between fresh and various aged TWC is outlined.

2. EXPERIMENTAL

2.1. Catalysts. TWC used in the present study are commercially available monoliths, from the same manufacturer, with around 20 weight % of washcoat (3.6 weight % of cerium) loaded with 40g/fi 3 of precious metals (PM), with a Pt~d/Rh ratio of 5/0/1. Three TWC were studied:by the various analytic methods ( sections 2.2 and 2.3): a fresh catalyst (42 m2/g), a 130 000 km vehicle aged, and a catalyst treated 24 h in air at 1100~ (3 m2/g). Two samples were picked from the 130 000 km catalyst: at the inlet (17 m2/g) and at the outlet section (15 m2/g). Four solids were studied only by 02 TPD and H 2 TPR: a washeoated eordierite without any PM, a TWC treated 4h under N 2 at 1050~ a commercially available catalyst 0.5% Pt/A1203 and a sample of pure CeO 2 (4.4 m2/g).

263 2.2. Light-off temperatures and vehicle emissions. The light-off temperatures (25% of conversion) were determined on a laboratory catalytic evaluation bench, using a F.T.I.R. spectrometer as detector [8]. The composition of the reactive mixture was: 14%CO2, 10%H20, 0.8%02, 0.4%CO, 950 ppm NO, 375 ppm C3H6, 125 ppm C3H8 . The emissions (expressed in g/kin) of CO, NOx and hydrocarbons (HC) during an ECE-EUDC cycle were measured on a 1.9L MPFI engine. The fresh TWC and the air aged catalyst have been previously treated on an engine test bench (4 h at 550~ R=I). 2.3. 0 2 TPD and H 2 TPR. The gas flow regulator and control system, the quartz microreactor and the analytic system (mass spectrometer) are identical to those used previously described [9]. During the H 2 TPR experiments, a second liquid nitrogen trap is inserted after the reactor in order to remove the water. The following procedures are used. The solids are dehydrated at 600~ under helium flow (30 cm3/min). The temperature is increased, at 25~ from room temperature to 600~ The solids are treated l h under 02 at 600~ and cooled down in 02 to 25~ After a purge with pure helium, the TPD (25- 900~ 25~ is started and the desorption of 02 is continuously recorded by mass spectroscopy (intensity of the peak m/e=32). The same procedure is used for the TPR experiments but after the helium purge at 25~ a reactive mixture, either 3% or 10% H2/He, is passed over the solids and the temperature is increased up to 900~ (25~ The consumption of hydrogen is recorded by mass spectroscopy (intensity of the peak m/e= 2). The experimental data give the amounts of oxygen desorbed and hydrogen consumed expressed in micromole per gram of catalyst (respectively lamolO/g and ~tmolH/g).

3. RESULTS. 3.1.02 TPD. 3.1.1. Fresh catalyst. The TPD spectrum carried out on a fresh catalyst, is shown in Fig. 1. Four oxygen desorption peaks are observed: a first small peak centred at Tm= 112~ two distinct peaks at Tm= 478~ and Tm= 725~ and a shoulder at Tm= 765~ The temperatures Tm and the total amount of oxygen desorbed are indicated in Table 1 (column 2). The amounts of oxygen evolved in each peak (assumed symmetric) are respectively: 0.07, 5, 7 and 12 lamoleO/g. The cerium content of this solid is 3.6 weight % (around 250 lamoles of CeO2 oxide/g of catalyst).

264 Therefore, it seems that the total amount of oxygen desorbed (241amol/g) during the TPD (20% considering the formation of Ce203), is more representative of a desorption than a bulk decomposition of the support. This total amount of 02 desorbed can be compared with the chemisorption data on TWC without nickel oxide [4].

02.

02. DESORPTION RATE (p.molO2,s)

0.06

OESORPT[ON RATE (pmo|O2.,sb

0.06 ! $36 765

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0.04

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o.o4 ~-

/

J f

/

0.02 ~f

0.02 | .

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J

i. I25 , .

9

200

400

600

$00

TEMPERATURE (oC3

Fig. 1 902 TPD spectrum of the fresh TWC

0

'

200

~0

/

~6[.../

600

$00

1000

TEMPERATURE (*C3

Fig. 2:02 TPD spectrum of the washcoat without PM.

In order to distinguish the oxygen species linked to the washcoat from those that may be assigned to the presence of metals, a TPD have been performed on the washcoated cordierite without any PM. The TPD spectrum (Fig. 2) shows three desorption peaks at Tm= 125~ Tm= 561 ~ and Tin= 836~ The amounts of oxygen evolved are respectively: 0.07, 2.1 and 9 ~molO/g. The main difference between the TPD spectra of the two solids (TWC and washcoat) is due to the disappearance of one of the two peaks at high temperatures. Likewise, an oxygen TPD have been carried out on the 0.5% Pt/A1203 solid. The spectrum (Fig. 3) indicates two distinct desorption peaks centred respectively at Tm= 489~ (2.3~molO/g.) and Tm= 687~ (11.6~molO/g.). The peak at Tin= 489~ is similar to the peaks observed on the washcoat at Tm=561 ~ and on the flesh TWC at Tm=478~ It can be observed that the TWC gives two peaks at high temperatures (Fig. 1) whereas the washcoat without PM (Fig. 2) and the

265 0.5% Pt/AI20 3 catalyst (Fig. 3) give only one main peak with different values of Tm (respectively 856~ and 687~ 02 DESORPTION RATE (ltmoiO2/s)

0.06

687 0.04

0.02 [

t l . . . .

0

L..._

2OO

_

400

600

800

TEMPERATURE (~

Fig. 3:02 TPD spectrum of the 0.5% Pt/A1203 solid

3.1.2. Aged catalyst. The amounts of desorbed oxygen, and the temperatures Tm of the peaks for the aged solids are presented in Table 1. The two samples of the vehicle aged TWC give similar results. The ageing of the TWC leads to a) a decrease of the total amount of desorbed oxygen, especially on the air aged solid and b) a disappearance of the first peak. The amounts of oxygen in the second peak are: 2.9, 0.4 and 1.4 lamolO/g respectively for the N2, air and vehicle aged TWC. On the air aged solid, the third peak appears as a small shoulde and the amount of 02 is included in the last peak. The amounts of oxygen detected in this third peak are 2 and 2.3 lamolO/g respectively for the N 2 and the vehicle aged TWC. The amounts of oxygen evolved in the fourth peak are respectively: 5, 1.1 and 6.1 lamolO/g for the N2, air and vehicle aged TWC. 3.2. H 2 TPR. 0 2 TPD experiments carried out on the various TWC, indicate the presence of four oxygen species for a total amount of 24~tmol/g for a fresh TWC. This study

266 is completed by H2 TPR experiments characterization of the oxygen species.

which is an other method

of

3.2.1. Fresh Catalyst. Figure 4 gives the H2 TPR spectrum obtained on the washcoat without any PM with a 3% H2/He mixture. Two major reduction processes are observed. The first one appears as a weak H 2 consumption peak centred at Tm= 115~ The second process gives poorly resolved peaks and shoulders at Tm= 470~ 695~ and 870~ which are due to various species exhibiting gradually increasing activation energies of hydrogenation. The reduction of the solid is incomplete at the final temperature (900~

Table 1 9Characterization of 02 TPD spectra offresh and aged TWC.

Amounts of desorbed 0 2 (lamolO/g) Temperature (~ 1st peak 2nd peak 3rd peak 4th peak

Fresh TWC

4h in N 2 at 1050~

24h in air at 1100~

24

9.9

1.5

112 478 725 765

572 741 819

500 750 830

130 000 km vehicle aged Inlet Outlet 9.8

9.8

48O 740 813

In order to identify the cerium oxide contribution on the H 2 TPR spectrum of the washcoat (Fig. 4), a TPR have been carried out on pure CeO2 oxide. The spectrum obtained (Fig. 5), indicates two reduction processes. The first one appears, as a well defined H 2 consumption peak at Tm= 604~ (169 lamolH/g). The second process is noticed over a wide range of temperatures (T> 650~ and is incomplete at 900~

267

TIgMPF.II~'rURlgI ~ 100

300

:500

TEMPERATURE(*C~ 700

900

0

0

0.2

I O0

3OO

870 e~

0.4

ff

7OO

9O0

17\

0.2

470 6 9 5 ~ ~

500

i0.4

6O4

0.6

0.6

Fig. 4: H 2 TPR spectrum of the washcoat without any PM

Fig. 5:H2 TPR spectrum of the Ce02 solid

T E M P E R A T U R E (~ 100

300

500

700

900

J

:~

O.2

.~

20 15

100 ~ 50

5 4/ ,

0

o

,

2;0

,

460

,

660 T/~

,

860

,

1(~0

1200

Figure 1. Oxidation of amorphous PdZr3 alloy in air investigated by DTA and TG. Conditions: heating rate, 5~ min-1; air flow rate, 30 ml min-1; sample weight, 52 mg.

288 The loss of weight occurring at ca. 900~ is due to the decomposition of PdO. The bulk structural changes of the glassy alloy were followed by XRD. Figure 2 depicts the XRD patterns of the precursor alloy before and aider oxidation, and after use of the samples in long term CO oxidation tests.

*

4

'

#

3

#

2

tt

9

20

I

30

'

I

'

40 20

I

"

I

50 60 /degrees

'

I

70

'

80

Figure 2. Bulk structural properties of glassy PdZr3 metal alloy and Pd/Zr02 catalysts. XRD patterns (CuKa) of glassy PdZr3 alloy (trace 1); PdZr-i (trace 2); PdZr-a (trace 3); PdZr-i after reduction in hydrogen (trace 4) and PdZr-c after reduction (trace 5). Denotation of reflections: * Pd, # PdO, + Zr02 monoclmic, "Zr02 tetragonal, ~PdZr2 and Zr. The XRD patterns of the in situ (PdZr-i, trace 2) and air-oxidized (PdZr-a, trace 3) alloys do not indicate significant bulk structural differences between these catalysts. After oxidation of the alloy under reaction conditions (m situ) as well as in air, a solid made up of PdO and monoclinic and tetragonal ZrO2 was formed. After reduction in hydrogen only reflections due to metallic palladium and zirconia phases were detected by XRD (trace 4). The XRD pattem of the coprecipitated catalyst (PdZr-c, trace 5) show palladium reflections indicating the presence of palladium crystallites, while the reflections due to zirconia phases are greatly broadened, which suggests amorphous phases. XRD line broadening and electron microscopy indicated that the catalysts prepared by oxidation of the glassy alloy were made up of small poorly crystalline palladium domains of about 5-7 nm lateral dimension. These domains were fidly integrated in predominantly amorphous zirconia. Although the coprecipitated catalyst contained palladium particles of about similar size (8 nm),

289 its structure differed significantly from the catalysts prepared from the glassy metal alloy. The palladium and zirconia domains were not intergrown as was observed wi~ the alloy derived catalysts. The bulk structural changes of the glassy Pd-Zr alloy induced by the oxidation were accompanied by large morphological and textural changes of the samples. Textural properties of the alloy-derived Pd/ZrO2 catalysts (PdZr-i and PdZr-a) and the coprecipitated Pd/ZrO2 (PdZr-c) are listed in Table 1 together with the corresponding properties of the palladium powder (Pd-p).

Table 1 Textural properties of the Pd/Zr02 catalysts prepared by oxidation of the glassy alloy (PdZr-i, PdZr-a) and by coprecipitation (PdZr-c). Pd-p denotes the pure palladium powder reference.

PdZr-i PdZr-a PdZr-e Pd-p

BET-surface area m2g-1 61.3 48.4 96.2 4.0

Pd-surface area a m2g-1 5.7 5.1 9.5 1.7

dispersiona %

Pd content %wt

5.7 5.2 7.9 0.4

22.3 22.3 30.4

a derived from CO chemisorption measurements as described in ref. [5]. Note that the coprecipitated Pd/ZrO2 catalyst had the largest BET and palladium surface areas. The procedure used to oxidize the Pd-Zr alloy had a significant influence on the textural properties of the final Pd/ZrO2 catalyst. Larger surface areas were obtained with in situ oxidation. Interestingly, with all three Pd/ZrO2 catalysts the BET/Palladium surface area ratio was approximately 10:1. The relatively low palladium dispersion is not surprising considering the high palladium content of the samples.

3.2 Catalytic properties CO oxidation: The temperature dependence of the CO oxidation activities of the catalysts are compared in Figs. 3A and B, and Fig. 4. The overall activities of the catalysts decreased in the order: PdZr-i ~ PdZr-a >PdZr-c > Pd powder, as indicated by the Arrhenius plots depicted in Fig. 3A and the conversion versus temperature plots shown in Fig. 3B. Significant differences were also observed for the activation energies. For both alloy-derived catalysts the activation energy,

290 determined from experiments with less than 10% conversion (Fig. 3A), was 58 + 3 kJ mol-], whereas for the coprecipitated catalyst (PdZr-c) and the palladium powder it amounted to 36 + 0.5 kJ mol-1 and 108 + 1 kJ mol-1, respectively. 9

!

d/

.

-18.0 -18.5 ~ -19.0 ~ -19.5 -20.0 2.4'215

2.6

100 80

312 (1000/T)/K

'' 7--:J~ A..~

B

~--

60 ~9

40 20

ol

314 "1

316

..0.

,

[] ~/ acre ~/a

.~--'r'~

.

X

/D []

318

- - - - - PdZr-i - - A - - PdZr-a - - o - - PdZr-c --zX-- Pd-p

o

[]

~ "1

A

'

dO

"

T/~

1 89

'

160

'

200

'

Figure 3. Temperature dependence of CO oxidation rate observed over Pd/Zr02 catalysts derived from glassy Pd-Zr alloy and reference catalysts. A) Arrhenius plots; B) CO conversion versus temperature. Conditions: standard feed gas mixture, 178.5 ml mm-1. Note different scale of the Arrhenius plots shown in Fig. A.

291 The activation energy determined for CO oxidation over the palladium powder is comparable to that reported for palladium wires, which is in the range of 101 kJ mo1-1 [9] to 125 kJ mol-1 [10]. The oxidation of CO over palladium was shown to be structure-insensitive [11,12]. The comparative catalytic studies presented here indicate that the interfacial contact of the palladium particles with the zirconia exhibits a strong influence on the catalytic behaviour of the palladium phase. Note that pure zirconia showed no activity for CO oxidation at the conditions used in this work. CO turnover frequencies (TOF) based on the determination of the accessible palladium atoms by CO chemisorption indicated roughly similar activities for the Pd in the alloy derived catalysts, while the TOF of the eoprecipitated catalyst was much lower. This is illustrated in Fig. 4. This behaviour is attributed to the marked structural differences of these catalysts. In our previous work [5,7] we have shown that catalysts derived by in situ oxidation from a PdZr2 alloy consisted of intergrown poorly crystalline domains of palladium and zirconia phases, resulting in an extremely large interfacial contact area between the active Pd and the zirconia phases. Such structural characteristics are not obtained with impregnation [5] or coprecipitation, as revealed by high resolution electron microscopy. The large interfacial area has been suggested to facilitate the oxygen transfer through the zirconia- palladium interface [5,7].

Q

•

5 4

m~ PdZr-i

3

A

PdZr-a

n--

PdZr-c

2

A"

~~~~J= 9 D

__D~D~D~D~D--O

o I

-20

I

0

I

20 T/~

~

5-

O----D-D----D I~D I

40

,

m

~o I

60

Figure 4. Temperature dependence of turnover frequencies (TOF's) for CO oxidation determined for Pd/Zr02 catalysts derived from Pd-Zr alloy and corresponding coprecipitated catalyst. For conditions, see fig. 3.

292 In the absence of oxygen, CO underwent disproportionation according to the equation 2 CO --> CO2 + C. As for CO oxidation, the alloy-derived Pd/ZrO2 catalysts were the most active catalysts, with CO conversions of 57% (PdZr-i) and 47% (PdZr-a) at 170~ Note that the CO conversion at this temperature was only 20% with PdZr-e, and the palladium powder (Pd-p) was inactive for CO disproportionation under these conditions. The carbon formed during disproportionation of CO was partly incorporated into the palladium lattice, as the XRD analysis of the catalysts used for disproportionation tests revealed. The interstitial carbon was very reactive and could easily be removed by subsequent exposure of the carbon loaded catalysts to an oxygen containing atmosphere (O2/argon). Carbon dioxide is formed upon oxygen exposure at temperatures as low as 80~ [8]. However, the interstitial solid solution was found to be stable under a CO atmosphere up to about 400~ at higher temperatures it decomposes to elemental palladium and carbon. XRD and DTG investigations indicated that at temperatures above 150~ carbon was incorporated into the Pd lattice up to a maximum solubility corresponding to a PdC0.16 phase [8]. Below 100~ there was no significant carbon incorporation into the catalyst PdZr-i. Figure 5 illustrates the carbon incorporation by comparing the XRD patterns of the alloy-derived catalyst PdZr-i before and after exposure to CO disproportionation conditions for 18 hours at 170~

CO

disproportionation:

~-

"A"

+

!

20

'

30

'

w

4O

5'0

'

60

2 - (9 / d e g r e e s

Figure 5. XRD patterns (CuKa)/ of reduced catalyst PdZr-i before (trace 1) and after (trace 2) exposure to CO disproportionation conditions: 1730 ppm CO in argon, 170~ for 18 hrs; * Pd, + Zr02 monoclinic.

293 P d Z r - c s h o w e d significantly l o w e r c a r b o n i n c o r p o r a t i o n u n d e r the s a m e e x p e r i m e n t a l c o n d i t i o n s , w h e r e a s no C O d i s p r o p o r t i o n a t i o n and carbon i n c o r p o r a t i o n c o u l d be o b s e r v e d w i t h the p a l l a d i u m p o w d e r b e l o w 4 0 0 ~ Thus the i n t i m a t e i n t e r a c t i o n o f p a l l a d i u m a n d z i r c o n i a s e e m s to be crucial for the high C O d i s p r o p o r t i o n a t i o n activity o b s e r v e d w i t h the c a t a l y s t s d e r i v e d f r o m the g l a s s y alloy.

2000

--~

02 . A

,

.

,

CO .

,

.

,

u~-t--q

.

,

.

,

.

,

.

,

.

'CO

~1500

2

CO-

...................... 0 2 "~ 1000

@

500

// /

D

\

..."

/

/

/

/

J !

0 0

2

4

!

.

6

9

~

"

I

10

8

t/min 2000

9 ,

9 ,

9 ,

.

,

I

'

12

'

I

9

I

14

16

1

'

18

20

9

/

1500

""~ 1000 t/ o

5oo

U ....... I

0

'

89 '

4

'

6

'

8

' 10

' 1'2 ' 14

~

I

16

'

I

18

'

20

t/n Figure 6. Behaviour of catalyst PdZr-i (A) and reference Pd powder catalyst (B) durmg alternate cycling between 02/Ar and CO/Ar feed. Conditions: 150~ 9 mm exposure to 1730 ppm 02 in argon, then 9 min to 1730 ppm CO in argon; flow rate, 178.5 ml min -1.

294 CO-O2 cycling: Figures 6 A and B illustrate the influence of the carbon storage on the behaviour of catalysts PdZr-i and the palladium powder (Pd-p) during forced cycling between CO mad 02 containing feed at 150~ As with the disproportionation experiments perfonned under stationary conditions, highest storage capacity for carbon was also observed with the alloy-derived catalysts (PdZr-i and PdZr-a). Figures 6 A and B depict one period of the cycling. The reactant gas was changed in 9 minutes intervals from O2/Ar to CO/Ar. The high CO2 production over PdZr-i during the CO/Ar feed period is attributed to the presence of adsorbed oxygen on the surface and to the disproportionation of CO. The carbon produced by this reaction and stored either as surface or interstitial carbon was oxidized in the subsequent O2/Ar period. 4. CONCLUSIONS

Palladium/zirconia catalysts prepared by oxidation of a glassy metal PdZr3 alloy possess superior activity for both oxidation and disproportionation of CO compared to corresponding catalysts prepared by coprecipitation and palladium powder. With the alloy-derived Pd/ZrO2 catalysts the disproportionation becomes significant at about 150oc, whereas with a coprecipitated palladium/zirconia catalyst mid palladium powder much higher temperatures are necessary. COdisproportionation is accompanied by carbon incorporation into the palladium lattice reaching a maximum solubility which corresponds to a PdCo. 16 phase [8]. The interstitial carbon is very reactive and easily removed by exposure of the sample to an oxygen containing atmosphere. These phenomena play an important role in explaining the dynamic behaviour of such catalysts trader conditions, where the reactant feed changes from CO to 02 rich periods, as realized during cycling between CO mad 02. The high activity of the Pd/ZrO2 prepared from the glassy metal alloy is attributed to its unique structural properties which provide an extremely intimate contact between the active palladium metal and the zirconia phase.

295 REFERENCES

7 8 9 10 11 12

A. Baiker, in Topics of Applied Physics, Vol. 72 (Eds. H. Beck and H. J. Gttntherodt), Springer Verlag, Berlin, 1994, 121-162 A. Molnar, G. V. Smith and M. Bartok, Adv. Catal. 36, 329 (1989) A. Baiker and D. Gasser, J. Chem. Soc. Faraday Trans. I, 85,999 (1989) A. Baiker, J. De Pietro, M. Maciejewski and B. Walz, Stud. Surf. Sci. Catal. 67, 147 (1991) A. Baiker, D. Gasser, J. Lenzner, and R. Schl6gl, J. Catal. 126, 555 (1990) A. Baiker, M. Maciejewski, S. Tagliaferri, Ber. Bunsenges. Phys. Chem., 97, 286 (1993) R. SchlOgl, G. Loose, G. Wesemalm, A. Baiker, J. Catal. 137, 139 (1992) M. Maciejewski and A. Baiker, J. Phys. Chem. 98, 285 (1994) G. M. Schwab and K. Gossner, Z. Phys. Chem. Neue Folge, 16, 39 (1958) Y. F. Yu Yao, J. Catal. 28, 1 (1979) T. Engel and G. Ertl, Adv. Catal. 28, 1 (1979) S. Ladas, H. Pappa and M. Boudart, Surf. Sci., 102, 151 (1981).


A. Frennet and J.-M. Bastin (Eds.) Catalysis and Automotive Pollution Control Ill Studies in Surface Science and Catalysis, Vol. 96 9 1995 Elsevier Science B.V. All rights reserved.

297

COMBUSTION OF M-XYLENE OVER Pd CATALYSTS DERIVED FROM AMORPHOUS Pd2NisoNb48 ALLOY L~iszl6 B o r k 6 , H u a Z h u a , Zolt~in S c h a y , Istv~in N a g y , A n t a l L o v a s b a n d L~iszl6 G u c z i

Department of Surface Chemistry and Catalysis, Institute of Isotopes of the Hungarian Academy of Sciences, P. O. Box 77, Budapest Hungary, H-1525; a On leave from Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan, Shanxi 030001, P. R. China; b Research Institute for Solid State Physics of the Hungarian Academy of Sciences, P. O. Box 49, Budapest, Hungary, H-1525

ABSTRACT

Oxidation of 0.05-0.1% m-xylene in 2.5-4.0% oxygen/nitrogen mixtures has been studied as a model reaction for the oxidation of aromatics in automotive exhaust gases over Pd catalysts derived from amorphous Pd2NisoNb48 alloy. The alloy in the as quenched form was inactive because its surface was covered by an NbO x layer. On etching in 40% HF the top oxide layer could be removed as well as Nb was leached from the subsurface layers resulting in a Raney-type surface layer of Pd and Ni. This layer had high initial activity but sintered during reaction. The final activity developed at 673 K in the reaction mixture during the initial 10-20 hours of operation as Pd segregated to the outermost layer of the ribbon. This resulted in a catalyst where Pd oxide was embedded in partly crystallized niobia-nickel amorphous matrix. In this high activity state light-off temperatures were 523-573 K at 50,000 h-1 space velocity depending on the xylene concentration and the temperature ramp. In some cases hysteresis loops were also observed.

1.

INTRODUCTION

Metallic monoliths seem to be a good candidate for automobile exhaust catalysts because of their excellent thermal properties. However, it is difficult to

298 fix a stable washcoat containing the active metals onto a metallic monolith. A solution could be the application of noble metals incorporated into the monolith and being activated before use. Amorphous alloys offer a possibility to prepare new catalysts of this type as they form a single phase solid solution in which the noble metal content can be varied continuously even outside the solubility limit in the equilibrium state. Catalytic properties of different types of amorphous alloys have recently been reviewed [1,2]. The catalysts derived from ribbons of rapidly quenched FeB and FeNiB amorphous alloys showed superior activity in the CO+H2 reaction [3], nickel-base alloy catalysts were used for oxidation of CO by O2 and NO [4]. In all of the cited works the as quenched amorphous ribbons needed some treatment as acid etching or in situ oxidation to obtain high catalytic activity. On the PdZr alloys a surface layer of highly dispersed Pd supported on nanocrystalline ZrO2 was developed [5,6,7]. Similar transformation was observed on the NiZr alloys [8], showing that both Ni and Pd can be transformed into highly dispersed metals supported on porous ZrO2. Ni based amorphous alloy containing Pd in low concentration seems to be a good candidate for hydrocarbon oxidation as both metals are active in oxidation reactions [8]. In the present work from the possible Ni-based metal alloys the Ni50Nb50 composition has been selected as we have good deal of experience in its preparation. We replaced part of Nb by Pd and used Pd2Ni50Nb48 amorphous alloy ribbons as starting material for the oxidation of xylene. The latter reaction has been selected as a model reaction for the oxidation of unbumt hydrocarbons in automobile exhaust gases.

2. EXPERIMENTAL

Pd2NisoNb48 amorphous alloy ribbons of about 2 mm width and 0.020.03 1run thickness were prepared by melt spinning using a single copper roller. The ribbons were cut into pieces of 15-20 nun length, corrugated by tweezers, etched in a 40% HF solution for different times and rinsed in high purity water before the catalytic test. About 0.17 g of the ribbons were placed between quartz wool plugs into a quartz tubular reactor of 8 mm diameter having a preheating and mixing zone of over 100 ml. Inconel shielded NiCr-Ni thennocouples were introduced directly into the gas phase before and after the catalyst. The temperature was controlled by a temperature progra~runer. In addition to the isothermal mode, temperature ramps of 2-20 K/min were applied both in heating and cooling modes, m-Xylene typicaly in 0.065% concentration was added by a syringe pump into a preheated

299 N 2 make up gas flow of 20 ml/min before the reactor. N 2 and 0 2 flOWS were controlled by mass flow controllers. The contact time was varied between 0.30.03 s corresponding to gas flows of 100-1000 ml/min at a catalyst volume of 0.5 ml. A nondispersive IR analyser was used for CO and CO2 and an FID for hydrocarbon analysis. All relevant signals were collected by on line computer. The amount of CO2 formed was taken as a measure of the catalytic activity. XRD using a Philips machine equipped with Guinier camera and KRATOS XSAM XPS machine were applied for characterizing the catalyst before and after the catalytic test.

3. RESULTS

The phases found by XRD are listed in Table 1. In the ribbon without any treatment only amorphous NiNb phase was detected in the form of a very broad and diffuse peak, typical for amorphous alloys without any trace of crystalline Pd in it. On the shortest etching in HF solution trace amount of Nb20 5 phase could already be detected. The mnount of Nb205 showed no systematic change with the etching time. Etching for 15 min resulted in the appearance of broad Pd lines indicating the presence of small Pd particles. No attempt was made to estimate any crystallite size. In the catalyst which showed the highest catalytic activity diffraction lines of Nb20 5, crystalline NiNb compounds, traces of crystalline Pd as well as amorphous NiNb phase were found.

Table 1 XRD measurements of the Pd2Ni50Nb48 alloy submitted to different treatments Treatment

Phases determined by XRD

no

NiNb amorphous phase Nb20 5 (cryst) NiNb (tryst) & (am) the same as at 5 m Pd (tryst), Nb205 (tryst) NbNi (tryst) & (am) NbzO 5 (cryst) NbNi (cryst) & (am)

5 mfia ha HF before reaction 10 min in HF before reaction 15 min in HF before reaction

15 min ha HF after reaction

This indicates that the bulk of the ribbon remained in all amorphous state even after prolonged treatment in oxidizing atmosphere at 673-773 K.

300 XPS showed that the surface of the untreated ribbon was covered with an oxide layer in which only Nb in the +5 oxidation state could be detected. Nickel and palladium in the surface layer were present in trace amounts, although the main body of the bulk consisted of NiNb amorphous phase. On the other hand, on etching for 5 and 10 min the major surface components were Ni and Nb in oxide state. Pd became the prevailing component only after 15 min etching in agreement with XRD studies. After reaction Pd remained the major component on the surface mainly in PdO form and the other components disappeared from the surface. However this was not in contradiction with the XRD measurements because the bulk could be a partially crystallized NiNb alloy embedded in amorphous NiNb alloy the surface of which was fully covered with highly dispersed Pd oxide. The results of the catalytic tests are shown in Figures 1-5. In Figures 1-3 the effects of etching time, contact time and oxygen concentration are given during the first temperature ramp when the catalysts were in a low activity state. The effects of contact time and oxygen concentration are similar to those we observed on the palladium catalysts prepared by electroless deposition of Pd from PdC12 solution onto stainless steel sheets [10]. The only difference is the formation of CO even at high oxygen concentration at the low conversion side of the temperature ramp as given in Figure 4. The amount of CO decreases on increasing oxygen concentration as shown in Figure 3b. Note the small CO2 O.fiO . 0.4.0

0.60 ]

I

9-. ~

~176

"1

9

~0.40

o0.~0 Lp

.

.

...~

k~.g'~ o6c;L"oB 473

.-

',9"

~.

0

00

0

~ *9 ~ 0~ 0 0 0 0 0 o %~, ...,.~.d~.,=..u, ma .,:,ouo, &,

s73

Temperoture

6;3

,

o

o~-o :,;

,z o o

]

-.

0

0 0.20

.'..

00

O0

.

0

,

0.10

0.00

OO

+

9

9

, ,"

9 ~

:

]

"%"

(K)

o

9 -. "..

o~ , ,,

o

9 "

."."':~

o o

o

8P~

.

7~3

Figure 1. Effect of the etching time in the xylene oxidation to C02 + 15 min; 010 min, o 5 min; ,r as received; ~" thermal oxidation. Contact time O.06 s; temperature ramp 5 deg/min; xylene concentration 20 %

o.oo

4.73

573

Tempercture

673

773

(K)

Figure 2. Xylene oxidation to C02 with varying contact time: ~e 0.3 s; x 0.15 s; o 0.03 s. Etching time 15 mins. Temperature ramp 5 deg/min; xylene concentration 0.065 %, oxygen concentration 20 %

301 0.50

1.00 o o

o

o

o o

0.40

Oo

0.80 o

e?

o

b's 0.60

",EL,O.30

o

,D

0 0.40 c)

0.00

cI~

i . . . . . . . . . .

73

o

o o

o

~

r ....

573

Temperoture

§ x

0.10

,

o

0 O0

*

,e

o

o

OO 0 0 0 0 0 0

.

00.20

o

o

0.20

0

ee

ooooOO,&;

x"

oo0

9

673

7"73

(K)

9=

5"73

473

9

II.

...g . . . .

~ 1 7 6 1 7 6 1 7 6 1 7 6" 1~ 7, + 6 ~1 '7~ o6 1 7t 6 1 7 6

~ o . 2 ~ o . o og . g ; 99 .".'.'... . . . . ~ , : : ,* * :.* . . 0.00

. . . .J,

80000

%,

ooo

S73

7?3

TemperQture (K)

a

b

Figure 3. Concentration of C02 (a) and CO (b) as a function of oxygen concentration: o 4 0 % ; ~r 20 %, x lO %; + 5 %; ~"2.5 %. Etching time 15 rains. Temperature ramp 5 deg/min; xylene concentration 0.117 %, contact time O.06 s. 1.00

0.60 ]

ooooo

0.80

oo

~

oo o

o

o

O~2o

oo o

oo t

0

b~ 0 rO

0.40

eo

o

00.20 0.20

o oo

o

o

~.~.

4.73

-9. . . . .

~ > o . o . ~ ~'- - . " - . . . .

s~s s~s Temperoture ( K )

/'/

~176

......

77s

Figure 4. Typical curves of xylene oxydation on Pd2NisoNb48 type catalyst, o C02; ~ CO. Etching time 15 mins, temperature ramp 5 deg/min; xylene concentration O.117 %, oxygen concentration 20 %

o

0.00

473 -

-

ot

e

9t

r t

o

o

o~

o

t

o

o

oo o o o o o

oee o

0

ol

o

0.00

t

~0.40

0.60

(,D

o~ ~

o

9

o oo

t

573

~o t e~

Temperoture

673

(K)

773

Figure 5. High and low activity state of etched Pd2NisoNb48 catalyst. o high activity; ~- low activity. Temperature ramp 5 deg/min; contact time 0.06 s; xylene concentration 0.065 %; oxygen concentration 20 %

302 peaks at 523 K in Figures 2-4, which typically appeared during the first cycles only, indicating the disappearance of sites of high activity present after etching. These sites are different from the ones that developed on extended use as given in Figure 5. As expected, on increasing etching time (Figure 1) the initial activity increases as well. Catalysts in the as quenched form or oxidized in air only are practically inactive. An increase of the etching time over 15 min resulted in no further increase in the catalytic activity. Extremely long etching time resulted in the desintegration of the ribbon leaving some Pd powder as residue. On repeated cycling or keeping the catalyst under the reaction mixture for long time at 673773 K a high activity state develops. In Figure 5 the two states are compared as they were observed on the same catalyst. In both states hysteresis loops are observed between the heating and the cooling ramps, as indicated in the figure.

4. DISCUSSION

In the as quenched form the Pd2Ni50Nb48 amorphous alloy ribbons are inactive in the oxidation of xylene. In contrast to the PdZr and NiZr alloys, whose catalytic activity increased on oxidative treatment [5,8] the surface of the Pd2NisoNb48 alloy is covered with a compact NbOx layer, where the niobium is in the +5 oxidation state. This layer prohibits any further oxidation of the ribbon. It can be removed by etching in 40% HF, which dissolves oxides but does not attack metals during short etching. On increasing the etching time the initial catalytic activity increases but it still remains low. Some unstable active sites are also formed, giving rise to oxidation at 523 K but these sites soon disappear. The origin of the activity is probably the formation of a Rmaey-type surface layer consisting of high surface area Ni with some Pd acting as impurity. During the initial few hours on stream, the Raney-type Ni structure is sintered and at the same time NiO is fonned as the active component of the catalyst, resulting in a relatively low catalytic activity and the disappearance of the activity at 523 K. With extended time on stream, a high activity state develops, which can be interpreted by enriclunent of Pd in the outer layer as well as by the formation of a high surface area niobium oxide acting as a support for Pd and NiO. The bulk of the ribbon still remains in the amorphous state ensuring mechanical strength and a good heat conductivity. The hysteresis loops observed are due to therlnal effects as the width of loops in the high activity state is about 30 K in good agreement with the temperature increase along the catalyst bed measured by the two thermocouples placed before and after the catalyst. On cooling the heat of the reaction compensates for the decreasing inlet temperature and keeps the xylene conversion

303

high resulting in a narrow hysteresis loop in contrast to the Pd/stainless steel catalyst, where the loop was of 100 K wide [10] and surface initiated gas phase reactions also contributed to the hysteresis. ACKNOWLEDGEMENTS The authors are indebted to Dr.E. Zsoldos for the XRD measurements and to the National Committee for Teclmological Development for financial support.

REFERENCES o

2. 3. .

.

6. .

8. .

10.

J. C. Yoon, D. L. Cocke, J. Non-Cryst. Solids 79 (1986), 217. A. Moln~ir, G.V. Smith, M. Bart6k, Adv. Catal. 36, (1989) 329 L. Guczi, G. Kisfaludi, Z. Schay, A. Lovas, Appl. Surf. Sci. 35, (1989) 469. K. Teruuchi, H. Habazaki, A. Kawashima, K. Asami, K. Hashimoto, Appl. Catal. 76, (1991) 79. A. Baiker, D. Gasser, J.C.S. Faraday 1 85, (1989) 999. A. Baiker, D. Gasser, J. Lenzner, A. Reller, R. Schl6gel, J. Catal.,126, (1990) 555. H. Kimura, A. Inoue, T. Masumoto, Mater. Lett. 14, (1992) 232. B. Qixun, z. Baoying, L. Zhen, M. Enze, Appl. Catal. A. 85, (1992) 101. G. I. Golodets, "Heterogeneous Catalytic Reactions Involving Molecular Oxygen", Elsevier, New York, 1983 L. Bork6, Z. Schay, L. Guczi, submitted to Appl. Catal.


Substrates and

Washcoat Technologies




307

DESIGN AND P E R F O R M A N C E OF A CERAMIC P R E C O N V E R T E R SYSTEM S.T. Gulati, L.S. Socha and P.M. Then Cornmg Incorporated, Cornmg, NY 14831 USA ABSTRACT The preconverter is an essential element of exhaust gas treatment to help meet the tighter emission standards of TLEV and LEV levels. Its design must be so chosen as to meet the simultaneous requirements of compactness, faster light-off, low back pressure, high temperature durability and low cost. This paper presents design options and performance data for a ceramic preconverter system which meets the above requirements. In addition, the high temperature physical durability data for selected preconverter systems are presented. These durability, back pressure, light-off and aging data presented here clearly demonstrate that a properly designed ceramic preconverter system is a viable and cost-effective approach to meeting TLVE and LEV emission standards.

1 INTRODUCTION The present paper examines design considerations and presents performance data for a ceramic preconverter system which is being sought by the automotive industry, worldwide, to help meet tighter emission standards - notably those corresponding to TLEV and LEV standards. While Europe, Japan and North America have been experimenting with metallic converter systems for light-off application and have met with some success, they have uncovered certain limitations, namely lack of design flexibility, limited high temperature capability, rapid heat dissipation, and high cost [1-4]. Clearly, a ceramic alternative is needed to overcome these limitations. The successful performance of cordierite ceramic converter system over the past 19 years in a myriad of applications - automotive, light duty vehicles and trucks - has amply demonstrated its suitability as emissions treatment device [5]. Furthermore, new developments in the area of ceramic converter systems have helped extend their applicability to small engines, both two-stroke, used in motorcycles [6-8]. In addition to design flexibility, the ceramic converter offers higher offers higher use temperature, improved heath retention and lower system cost.

308 The preconverter system must meet the following requirements:

i)

it must be compact to fit the available space in the engine compartment; it must provide sufficient surface area for effective exhaust gas treatment; it must be light and well-insulated to reach the light-off temperature quickly; iv) it must retain and prolong the effectiveness of precious metal catalyst to meet TLEV and LEV emissions standards; v) it must endure high operating temperature (>1000~ while minimizing temperature gradients; vi) it must have high strength to withstand mechanical and thermal stresses under operating temperatures and vibrations; vii) it must be efficient in transferring exothermic heat to the main converter for good conversion activity; and viii) it must be easy to assemble in a low-cost durable package. ii) iii)

From automakers' point of view, a preconverter package designed and assembled in the above manner is readily implemented in the exhaust system. It also shortens the developmental cycle and reduces engineering costs--a most desirable combination for meeting legal and commercial requirements. This paper focuses on design and performance data of a ceramic preconverter system as function of substrate composition, size, cell geometry, cell density and catalyst formulation. The high strength, low porosity cordierite ceramic composition permits a thin wall catalyst support with the advantages of larger hydraulic diameter and lower back pressure compared with those attainable with the standard automotive substrate. Both cylindrical and eUipdc preconverters with volumes ranging from 0.29 liter to 0.74 liter have been catalyzed with two different catalyst formulations. Their light-off temperature, FTP NMHC emissions with bag 1 and steady state HC, CO and NO x emissions, following 60 and 120 hours of aging in 900~ rich-lean cycle, are presented [9,101. Finally, the measured pressure drop across the preconverter is presented as function of cell density, flow rate, gas temperature and converter size. Trade-offs in performance vs. durability vs. systems cost are reviewed. 2. DESIGN OF CERAMIC PRECONVERTER The design flexibility offered by ceramic substrates stems from the availability of several cordierite compositions [11-13] and well-established extrusion technology [141 which permit the choice of microstructure for optimum interaction with alumina washcoat as well as the choice of cell geometry with the desired geometric and physical properties. Table 1 compares the pertinent properties of two different thin-wall substrates of low porosity and high strength composition, EX-22, with those of standard substrates of EX-20 and EX-32 compositions [6, 151. The mechanical integrity factor MIF, thermal integrity factor TW, open frontal area OFA, geometric surface area GSA and Hydraulic diameter D h are performance parameters which depend on cell shape and size [16]. They are readily computed for a given cell geometry and are very useful for preliminary design. They have a direct impact on physical properties and converter pertbrmance. For example, the substrate strength crs is proportional to the product of MIF and wall strength ~w, i.e. ch = ko'w(MIF) Similarly, the thermal shock resistance, TSR, of ceramic substrates is given by

(t)

309 TSR = O's x TIF 2Ewaw , _~ m

xTIF 3E,~w , ~

square cell

(2)

triangular cell

(3)

In EQs 1, 2, and 3 k is a constant, Ew denotes wall modulus and a w its coefficient of thermal expansion. The pressure drop Ap across the preconverter depends on flow rate Q, hydraulic diameter D h, and open frontal area OFA, as follows: Ap =

Qe 4:~-d2 x OFA x I~

(4)

where d denotes substrate diameter and e its length. For a given space availability in the engine compartment, we assume a circular substrate of diameter d and length e with three different compositions and four different cell geomeTable 1 Nominal Properties of Standard and Thin-Wall Cordierite Substrates

Composition

Cell structure Ceil shape Wall thickness (mm) Open porosity Mean pore size (lam) Wall strength (MPa) Wall modulus (GPa) MIF Substrate strength* TIF TSR OFA (%) . GSA (cm2/cm 3) Avg. CTE @ 800~ (10-7/~ D s (mm) W~ll density (g/cm 3) . Substrate density (g/cm ~) Heat capacity of Substrate (cal/cm3~ Thermal diffusivity ( 10-3 cm2/s)

EX-20 (std)

EX-32 (std)

EX-22 (Thin-Wall)

]~X-22 (Thin-Wall)

400/6.5 Q 0.188 35% 3.0 20.3 26.1 0.025 73 k 6.9 110 k 73 27.4 6.0 1.106 1.61 0.43

236/11.5 A 0.292 42% 7.0 14.3 20.9 0.034 70 k 7.1 110 k 64 22.0 5.0 1.159 1.42 0.51

350/5.5 Q 0.140 20% 2.0 43.1 42.9 0.012 75 k 9.7 290 k 80 26.4 2.0 1.218 2.0 0.39

340/6 A 0.152 20% 2.0 43.1 42.9 0.013 81 k 11.3 254 k 76 28.9 2.0 1.056 2.0 0.49

0.11 4.65

0.12 4.08

0.10 5.13

0.10 4.08

CTE: Coefficient of Thermal Expansion * The constant k is a normalization constant to help compare strength of cordierite substrates with different porosity and cell structures.

310

(GSAx~s)

tries as shown in Table 1. For optimum light-off performance it must offer the greatest geometric surface area, highest strength and lowest density, i.e. the quantity ps must be maximized. Similarly, for optimum thermal shock resistance, its TSR must be maximized and finally, for low pressure drop the quantity (OFA x D~) must be maximized. Table 2 compares the calculated values of these parameters for the four substrates shown in Table 1. It shows clearly the superior performance of EX-22 substrates over that of standard substrates. Both the light-off performance and thermal shock resistance are 10 to 60% better than those of standard substrates. The back pressure reduction is significant for 350/5.5 O while that for 340/6 A compares favorably with EX-32, 236/11 A structure. 4. PHYSICAL PROPERTIES OF LIGHT-OFF SUBSTRATES The pertinent physical properties which impact the mechanical and thermal durabilities of substrate include biaxial compressive strength [17-19], high temperature modulus of rupture [20], elastic modulus, and thermal expansion curve as function of temperature [5, 6]. The biaxial compressive strength is a direct measure of substrate's ability to withstand radial mounting pressure during canning. To ensure long-term durability, the preconverter should be packaged in a tourniquet can with high and uniform biaxial compression facilitated by its circular contour. The biaxial compressive strength, which is critical for mechanical durability, was measured in a dual-band tourniquet fixture [19]. Five EX-22 substrates, 85.5 mm diameter x 120 mm long, having a volume of 790 cm 3 (0.79 liter), were wrapped in 3660 ffm 2, Series IV, intumescent mat and subjected to a uniform radial compressive stress until they failed. The choice of substrate size was dictated by both the genetic space envelope in the engine compartment and the total surface area required for light-off conversion. The 0.79 liter substrate is deemed adequate for fight-off conversion for engine displacements ranging from 2 to 3.5 liters. Table 3 summarizes the biaxial strength data for uncoated substrates. The strength values of 5 to 7 MPa for square cell substrate and 7 to 12 MPa for triangular cell substrate are nearly an order of magnitude higher than the mounting stresses during high speed canning. Furthermore, the biaxiai strength of coated substrates which represent the final product is 30% higher than that of uncoated substrate thereby making the safety factor even higher [21, 22]. Finally, the circular contour of preconverter permits a uniform radial mounting pressure which, in turn, enhances its long-term durability. ,,

Table 2 Comparison of Performance Parameters of Standard and Thin-Wall Cordierite Substrates

Table 3 Biaxial Compressive Strength of EX-22 Substrates (85.5 mm dia. x 120 mm long)

Composition

,,

EX-20 EX-32 EX-22 EX-22 400/6.50 236/11.5A 350/5.50 340/6.3A

.

350/5.7 UI (MPa)

340/6.3 zX (MPa)

.

.

.

.

GSA x crs Ps TSR

4480

2900

5075

4790

Min.

4.9

7.4

110 k

105 k

290 k

255 k

Mean

5.7

10.1

OFA x D~

0.893

0.856

1.187

0.853

Max.

6.8

12.6

311 The modulus of rupture (MOR) of above substrates was measured in four-point bending using rectangular bars, 2.5 cm wide x 1.25 cm thick x 10 cm long, cut from the substrates in both axial and tangential directions [23]. These measurements were carried out at 25 ~, 700 ~ and 900~ with latter temperatures representing the maximum operating temperature of peripheral region of preconverter which experiences the highest thermal stress in service. The MOR data for 350/5.7 square cell substrate and 340/6.3 triangular cell substrate are summarized in Tables 4 and 5. Figure 1 which is a Weibull plot of axial MOR data at 25~ demonstrates the unimodal nature of strength distribution with Weibull slope of 13 equivalent to a standard deviation of 8% [241. It should be noted in Tables 4 and 5 that MOR values increase with temperature due to both the absence of stress corrosion and healing of microcracks in the porous cordierite body at high temperature [25]. Such an effect allows higher operating stresses and is beneficial to preconverter's long-term durability. A comparison of Tables 4 and 5 shows the triangular cell structure to be 20 to 40% stronger than the square cell structure which affords it a superior mechanical reliability to combat canning, vibrational and Table 4 impact loads in service. Finally, the MOR High Temperature MOR Data for values will show further improvement of EX-22, 350/5.7 UI Substrates (Mean Values) about 30% after the substrates are washcoated with high surface area 7-alumina washcoat No. of [21,22]. Temp. Specimens Axial MOR Tang. MOR The elastic moduli and thermal expansion (~ (MPa) (MPa) curves in the axial direction of above substrates are shown in Figures 2 and 3, respec25 10 2.98 1.23 tively, over a temperature range of 25 ~ 700 10 3.13 1.31 1000~ In view of its more rigid structure, the triangular cell substrate is approximately 900 10 3.30 1.36 10% stiffer than the square cell substrate. This is consistent with its higher MOR and biaxial compressive strength compared with 99 EX-22 subsCrate those of square cell structure. It should be , 9 j9 350/5.7 square cell 9 gO noted in Figure 2 that the moduli remain relair structure . 8O tively constant up to 600~ and then increase - A 340/6.3 triangular ==~ cell structure .,~6O with temperature due to stiffening associated 9 with the healing of microcracks. The increase "-" 4 0 .a in moduli implies higher thermal stresses at ~ ,d -O= 2 0 operating temperature which are self-cornL. ,,,

-

o

10

;

,= tL

5

.:

a.

i,.

r

/ !

!

I

Table 5 High Temperature MOR Data for EX-22, 340/6.3 A Substrates (Mean Values)

/ !

!

!

!

1.5 2 2.5 3 3.5 4 4.5 Axial Modulus of Rupture (MPa)

Figure 1. Weibull plots of axial MOR data at room temperature for EX-22 substrates with 350/5. 7 ~ cell anti 340/6.3 A cell structure

No. of Temp. Specimens Axial MOR Tang. MOR (~ (MVa) (MPa) 25

10

3.50

1.32

700

10

3.70

1.49

900

I0

4.55

1.53

312 p e n s a t e d by the c o r r e s p o n d i n g EX-22 subs~ate increase in MOR values noted ear13 " 3 5 0 / 5 . 7 square cell structure lier. "g 93 4 0 / 6 . 3 triangular cell structure The expansion data in Figure 3 ~ 12 c l e a r l y show that both 350/5.7 ,, square cell and 340/6.3 triangular ~ 11 II =o cell structures have identical therreal e x p a n s i o n s over the entire ~ lO o temperature range of interest (25 ~ = a~ 1000~ Furthermore, the expan[] 9 sion curves of EX-22 composition _ca go t h r o u g h a m i n i m a at 300~ "~ 8 < II I - i ' l ' l ' l ' m ' I ' l " i " l " implying that the thermal stresses ! = . 1 , I , I j ! = ! associated with temperature gradi7 200 400 600 800 1000 e n t f r o m c e n t e r to p e r i p h e r a l 0 Temperature ('C) region will shift from tension at the center to tension at the periphFigure 2. Temperature dependence of axial elastic e r y as the c e n t e r t e m p e r a t u r e moduli of EX-22 substrates with 350/5.7C1 cell and exceeds 300~ during light-off. At 340/6.3 A cell structure temperatures approaching 1000~ the thermal stresses in the peripheral region will be dictated by radial temperature gradient, absolute thermal expansion, and elastic moduli. It should be noted, however, that the EX-22 composition has one-third the expansion coefficient of standard cordierite composition EX20 [6] ; see also Table 1. The low expansion behavior of EX-22 substrates makes them thrice as durable as EX-20 substrates and hence ideal for light-off application. -

/:

//

L_

5. P A C K A G I N G DESIGN Due to severe operating conditions in close-coupled light-off application, a robust mounting system is required for the preconverter to survive 160,000 vehicle kilometers. Such a system, shown in F i g u r e 4 includes a new intumes500 EX-22 substrate cent mat, InteramrM 100, 400 which is protected on the 0 front and back edges by 300 ca high t e m p e r a t u r e seals. Q. x The seals are flexible dur'" E 200 -U ing a s s e m b l y and are r E "E 100 =.... a t t a c h e d to the m a t to facilitate mounting and to I-.o 0 .,~ ensure thermal integrity X -100 under operating conditions. The i n t u m e s c e n t -200 temperature range of this ! , ! , I I I , 1 , I , 1 , I , 1_ , -300 mat is broader than that of 100 200 300 400 500 600 700 800 900 1000 standard Interam TM mats Temperature (* C) used in underbody applications [7, 8, 25, 26]. This mat Figure 3. Axial thermal expansion curves for EX-22 substrates begins to expand at 40~ with 350/5.7 ~1 cell and 340/6.3 A cell structure l o w e r t e m p e r a t u r e than

313 that tbr standard mats. Similarly, its upper temperature capability is 50~ higher than that of standard mats. The high temperature seal rigidizes when it is heated during the first operating cycle of the converter and forms a strong barrier thereby protecting the mat from potential erosion caused by impingement of hot exhaust gases. The seal consists of glass flit, with low softening temperature, an organic binder and other inorganic fillers. The i n o r g a n i c materials fuse together at a moderate temperature to form a solid body which is relatively impervious to exhaust gas pressure pulsations and which reduces the temperature of the mat edge. A preconverter package of the design shown in Figure 4 was assembled with I n t e r a m TM 100 mat, c o m p r e s s e d to a mount density of 1.2 g/cm 3, and subjected to durability testing discussed in next section.

~

(a)

93.0

mm

dla.

2.58

mm

gap Detail A

~~-

lm.

-45

(b)

"" ...........

i ....

, ............

130 mm

mm

Detail

~+-"

,',-

~1

.~ -.

A 4

mm---

/ "/ High temp. s e a l - -

6. P E R F O R M A N C E DATA In this section we will summarize the performance data consisting of i) ii) iii) iv)

Figure 4. a) Schematic of packaging design for preconverter; b) detail of mat~seal attachment with wire screen wrap

physical durability; back pressure across preconverter; emissions reduction with preconverter; effect of aging on FTP emissions.

The performance tests were carried out at three different independent laboratories using both the ceramic and metallic preconverter systems. The latter comprised of a commercially available Fe-Cr-A1 alloy support with 400/2 ~ cell structure and measured 93 mm diameter x 90 mm long. Both preconverters had identical catalyst loading (40 g/ft 3, TWC) with a Pt:Rh ratio of 5:1. 6.1. PHYSICAL DURABILITY

The physical durability of EX-22, 350/5.7 CI ceramic preconverter was assessed in two different tests. The first of these was a high temperature vibration test, using an exhaust gas generator and electromagnetic vibration table [27], under the following conditions: Exhaust Gas Temperature Acceleration Frequency

1030~ 45 g's 100 Hz

314

F

~F

i i

I

l.zpm x

=dl

J

|

///

////'

/ / / / / / / /

d

Figure 5. Schematic of axial push-out test

Figure 6. Force balance in axial direction during push-out test

The test was run for 100 hours and cycled back to room temperature 19 times with no failure detected in the mounting system. The ceramic substrate maintained its original position, the seals rigidized and remained attached to the mat, and the mat was not eroded. The robustness of the mounting system was also verified via an axial push-out test shown schematically in Figure 5. The push-out force F required for relative motion between the substrate and mat is related to mounting pressure Pro, friction coefficient la (~ 0.25) and substrate dimensions as shown in Figure 6. The push-out force F was measured as function of mat density Pm and the mounting pressure Pm was calculated from EQ 5. The push-out speed was held constant at 25 ram/rain. The data, plotted in Figure 7, are consistent with the empirical equation relating mount density to mounting pressure [26]

~

o 7 I-

O~

~6@

u~ @ lb..

Pm = Le-6"7/pm

8

t 67 ~Z

5-

5

Pm

4"

u 0 u_

"4.*,. 0

g" 3 -

--"

,,, 2

--2et

3

l -I

=! 1 0

t

1.0

!

!

!

1.1 1.2 1.3 Mount Density Pm (g/cm3) Figure 7. Axial force and mounting pressure during push-out test as fimction of mount density

(5)

in which the c o n s t a n t ~, depends on push-out speed. For the push-out speed of 25 turn/rain., ~, = 1060 kg/cm 2. At higher s p e e d s L can a p p r o a c h a value of 4500 kg/cm 2 and result in 4x higher pressure which, however, lasts for a very short time (few seconds) since the mat relaxes due to its viscoelastic behavior. The coated substrate can readily withstand a mounting p r e s s u r e of 30 k g / c m 2 or 3MPa for short duration since

315

5MPa; see Table 3. The mat density of 1.2 ffcm 3 was selected to ensure a mounting pressure of 4-5 Kg/cm 2 which is needed tbr mechanical integrity. The insulation property of Interam TM 100 mat is critical to the thermal integrity of ceramic preconverter evaluated by measuring the radial temperature gradient in the preconverter during the exhaust gas simulation test using compressed air and a natural gas burner; see Figure 8. The EX-22, 340/6.3 triangular cell substrate (85.5 mm diameter x 120 mm long) was packaged in a stainless steel can using a Interam TM 100 mat and the stuffing technique. The inlet gas temperature was 1030~ and the flow rate was 1.13 m3/min, corresponding to a space velocity of 86,000/hr through the 0.79 liter substrate. The temperature vs. time output at the center and peripheral regions of preconverter and the stainless steel shell is plotted in Figure 9. According to Figure 9, a temperature gradient of 130~ was measured between the center and peripheral regions during exhaust gas simulation test. This is relatively low indicating excellent insulation property of Interama'M 100 mat. Furthermore, the heat retention afforded by the mat keeps the preconverter hot and efficient during coldstart conditions. The improved insulation property of the mat also maintains the shell temperature at a reasonably low value thereby minimizing shell distortion due to mounting pressure. The typical temperature drop across the mat during exhaust gas simulation test is 360~ as shown in Figure 9. This is a significant temperature drop which protects preconverter components, including the mat itself, from high temperature degradation. 6.2. BACK PRESSURE

Sd~ll

500

O. E 400

~" 3 o o 200

100 0

10

Tlme (mln.)

20

30

Figure 9. Time variation of temperature of sheU and substrate periphery during exhaust gas simtdation test

The back pressure was measured for three different preconverter assemblies (all catalyzed) in a chassis dynamometer test (4 liter, 6 cyl. engine with PFI). The three preconverters had identical outside dimensions, namely 93 mm diameter x 90 m m long, but d i f f e r e n t cell structures and compositions:

316 i) 350/5.7 square cell structure of EX-22 cordierite ceramic composition; ii) 340/6.3 triangular cell structure of EX-22 cordierite ceramic composition; iii) 400/2 sinusoidal cell structure of Fe-Cr-A1 metallic composition. The back pressure was measured with the aid of H20 monometers. In addition to pressure drop across preconverter, the total pressure drop from exhaust manifold to tailpipe was also recorded. The measured values are summarized in Table 6. It is interesting to note that under the specified test conditions the 350/5.7 El ceramic preconverter yielded 3% lower back pressure than the 400/2 ~ metallic preconverter. Similarly, the 340/6.3 A ceramic preconverter yielded 7% higher back pressure than the 400/2 7xTx metal preconverter. These differences are Table 6 attributed to both the back pressure parameter, Back Pressure Data for Three BPP, and frictional drag of catalyzed walls to Different Preconverters during gas flow which vary with cell structure. The Chassis Dynamometer Test @ 80 km/hr former is def'med by (93 mm diameter x 90 mm long prec0nverter with inlet gas temp. = 700~ BPP = O F A x I ~ (6) Total Back Cell Back Pressure Structure Across Preconverter Pressure whose values for uncoated substrates appear in (cm H20) (cm H20) Table 2 and are inversely proportional to measured back pressure data. It should also be 350/5..7 Q 32.5 68.0 ceramic noted that the back pressure across all three preconverters is approximately 47 to 50% of the 72.1 340/6.3 A 36.0 total back pressure from exhaust manifold to ceramic tailpipe. 400/2 7xTx 33.5 71.1 metallic 6.3. EMISSIONS REDUCTION wrrH PRECONVERTER

Configuration 1

Configuration 2

Configuration 3

i 20,

T

e40 mm

9 Gontlnuo~ emluk:m8 Wobe

Figure 10. Exhaust configurations during FTP test: 1) main converter only, 2) preconverter only, 3) main converter and preconverter

The catalytic efficiency of three different preconverters was measured on a 1994 vehicle powered by a 4 liter, 6 cylinder engine with port fuel injection. This vehicle's engine-out emissions were 2.3 g / m i l e N M H C , 16.9 g / m i l e CO, and 5.9 g/mile NO x. Three different exhaust configurations were employed during emissions testing using the FTP cycle [28-30]; see Figure 10. The main converter consisted of two ceramic substrates with a total volume of 3.2 liters. One of these was catalyzed with a Pt/Rh catalyst and the other with Pd only catalyst. The charac-

317

teristic d i m e n s i o n s and catalyst loading for the three preconverters Table 7 are summarized in Table 7. Figure Description of Ceramic and Metallic Preconverters 11 compares the tailpipe HC emis350 C] 340 A 400 sions with and without the ceramic ceramic ceramic metallic preconverter (350 CI), i.e. for conpreconverter preconverter preconverter figurations 1 and 3. It shows that the preconverter contributes to emis- Substrate sions reduction during the 40-120 Diameter 85.5 mm 85.5 mm 90 mm sec. interval. The FTP emissions are reduced significantly due to oxida- Substrate tion of HC and generation of Length 80 mm 80 mm 80 mm exothermic heat for faster light-off of main converter. This benefit is Outside Can 93 mm 93 mm 93 mm attributed to higher surface area, Diameter lower thermal mass, and close proximity of the ceramic preconverter to Wall 0.145 mm 0.160 mm 0.05 mm exhaust manifold which reduce the Thickness time for light-off temperature to 40 Catalyst sec. of cold-start. It is also clear in Loading 40 g/ft 3 40 g/ft3 40 g/ft 3 Figure 11 that after 120 secs, the 5:1 Pt/Rh 5:1 Pt/Rh 5:1 Pt/Rh HC emissions for both configura- PM Ratio tions are identical implying that the main converter is fully effective. Further reductions in the light-off time of preconverter, and hence in bag 1A emissions, are also possible by either moving it closer to the engine or using a different catalyst loading or formulation. For the tests described here the preconverter and main converter were located at a distance of 0.64 m and 1.22 m, respectively, from the exhaust manifold. To verify the onset of lightoff conditions, the ceramic pre700011"----- ENGINE OUT EMISSIONS converter was instrumented with 2.287 g/mi NMHC 10 chromel-alumel, Type K, 6000 - - - MAIN CAT. ONLY-TAILPIPE EMIS.-O.188 g/mi NMHC thermocouples and the temperatt:ll! ~.: R .... u~r-oF~a,,,N c,rI ture-time history was recorded 5000 I t : " /:~':t~, P.V'P.~ ~ps.,ONSI o. : -/' ~ u.,,:4g/m, r,M,~. I during the FTP cycle; see Figure 12. The temperature vs. time plot for the preconverter section, 2.5 cm from the entry face, is i o 3000 . , shown in Figure 13. It is clear from this figure that all of the Z O O 0 -rfive thermocouples are recording identical t e m p e r a t u r e s '~176176 "...!-.4,,...,,....ii-l, ,'r indicative of uniform, laminar, flow distribution. This is true for I I I I "1 ................... 0 20 40 60 80 I00 120 140 both the metallic and ceramic TIME (Seconds) preconverter systems. Figure 14 shows the t e m p e r a t u r e - t i m e Figure 11. Continuous HC emissions during cold-start curves for both ceramic and from engine and tailpipe with main catalyst only vs. main metallic preconverters prior to catalyst plus preconverter light-off. These data show that

318

I1.25 cm 5 ....

6

0----.0-----7, 13 8, 2, 4

9 =

I

10

_! vl

I_ I-

2.5 cm

1.25

cm

=

2.5 cm

Figure 12. Thermocouple locations for monitoring preconverter temperature during cold-start 800

*.., 6 0 0 rl;

~1--

500

re"

tu 4 0 0 G. 1~

w

I--

TCe7 TC'5, 9

300

200 1(3(3

[

0

25

]

50

[

[

]

75 i 0 0 125 TIME ( S e c o n d s )

!

150

I

175

!

200

225

Figure 13. Temperature vs. time during bag 1A portion of FTP cycle for EX-22, 350 0 ceramic preconverter section 2.5 cm from entry face 400 350

Inlet gas temp. --Metallic temp. 2.5 c m f r o m front

~" 300

_ C e r a m i c t e m p . 2.5 crn f r o m front

"" 250 e 200(11 k,. o

,,,- 1 5 0 -

Ceramic temp. 2 . 5 c m from exit Metallic temp. 2 . 5 c m from exit

E

~. l o o 50 5

10

15 20 25 Time (Seconds)

30

35

40

Figure 14. Temperature vs. time curves for inlet gas, ceramic preconverter and metallic preconverter prior to light-off

both preconverters heat up at a similar rate. Figure 15 shows the average internal temperature of ceramic and metallic preconverters. After the initial catalytic activity, the ceramic p r e c o n v e r t e r maintains an internal temperature only 20~ higher than that of metallic preconverter throughout the FTP cycle. However, Figure 16 shows that the average surface temperature of 409 S.S. can of ceramic preconverter is 200~ lower than that of metallic preconverter. This shows that the ceramic preconverter retains more heat in the exhaust stream thereby promoting early light-off of the main converter. The metallic preconverter, on the ohter hand, radiates heat to the s u r r o u n d i n g e n v i r o n ment with lower impact on light-off of main converter. 6.4. EFFECT OF AGING ON FTP EMISSIONS Four preconverters were aged simultaneously on a 7.5 liter, 8 c y l i n d e r engine with throttle body fuel injection. During aging the main c o n v e r t e r was mounted in series following the preconverter. Uniform mixing of exhaust gas was achieved by using a 15.2 cm transition from the exhaust pipe to entry face of the preconverter. The same transition was also used at the exit end of main c o n v e r t e r . L a m i n a r flow e l e m e n t s , downstream of each converter, were used to balance the flow through each con-

319

verter. The FTP emissions test used both the preconverter and main converter assemblies exactly as they were aged. The converters were aged for 60 and 120 hours using the aging cycle described in Table 8. This cycle was chosen because it exposes the catalyst to both lean and rich conditions for extended periods of time. It maintains a low inlet temperature to the catalyst minimizing thermal combustion in the exhaust system. Thermal reaction in the exhaust pipe is very difficult to control. With this cycle the temperature oscillations are created by the catalytic activity, which is a more appropriate and demanding test of the catalyst system. The catalyst performance was evaluated by using the U.S. Federal Test Procedure. S i n c e the key purpose of preconverter is to reduce the cold-start emissions, bag 1 of FTP cycle was split into two bags: bag 1A which represents 0 to 220 sec. and bag 1B w h i c h r e p r e s e n t s 220-505 sec. However, at t = 220 sec. the temperature of the main converter is relatively stable and sufficiently high to ensure rapid reaction kinetics. The effect of aging on FTP emissions was measured using exhaust configuration 2 (see Figure 10) with the 350 Q ceramic preconverter and 400 7x7~ metallic preconverter. The NMHC, CO and NO x emissions output from each of these preconverters are compared as function of their

Table 8 Aging Cycle for Preconverters ,and Main Converter Rich-Lean Aging

Inlet to Catalyst Lean Rich

A/F (Spindt method) A/F (A/F analyzer) THC (ppm) CO(%) CO 2 (%) NO x (ppm) Oxygen (%) Catalyst Bed Temperature (~

15.66 13.65 725 3.75 9.67 1125 4.2

12.38 12.50 1500 6.00 10.9 1440 0.7

900

650

800 .

.

700 .~600

.

.

.

.

.

.

Out of Catalyst Lean Rich

0 0.027

925 5.64

1000 1.5

0 0

900

650

.

.

3

500

:: oo 400

"400 rrn metallic

200 loo

0

I 20

I 40

., ! 60

! ! ,! I i l 8 0 100 120 140 160 i 8 0 Time (Seconds)

t 2 0 0 220

Figure 15. Average internal temperature for ceramic and metallic preconverters during FTP cycle (config. 2)

50O

~' 4 0 0 ",.,,, 3

O.

93 0 0 200

E

I~. 100 1

50

[

100

I

150

I

200 Time

I

t

250 300 (Seconds)

t

350

t

400

!

450

500

Figure 16. Average surface temperature of can for ceramic anti metallic preconverters during FTP cycle (config. 2)

320 aging time in Figure 17. The 7 I I | I I NMHC x 10 ~ [ ceramic and metallic precone 13co verters demonstrate equivalent ~s p e r f o r m a n c e with only six hours of aging. At this level, o the c e r a m i c p r e c o n v e r t e r reduced NMHC emissions by additional 5% compared with n._ metallic preconverter. How0 ever, after 60 hours of aging Ceramic Metal Ceramic Metal Ceramic Metal the metaUic preconverter was 6 6 60 60 120 120 55% less effective than the Aglng Time (Hrs) ceramic preconverter in reducing NMHC. At 120 hours of Figure 17. Comparison of FTP emissions from 350 0 aging the ceramic preconverter ceramic vs. 400 mTx metallic preconverter alone as continued to outperform the function of aging time (config. 2) metallic preconverter by 49% 0.20 l in NMHC reduction. This indi0.18 cates that the metallic precon0.16 verter suffered a partial loss of conversion activity during the E 0.14 6 to 60 hours of aging process. o.12 A possible explanation for this 0 0 . 1 0 is that the continued expansion ~E 0 . 0 8 z and c o n t r a c t i o n of metallic 0.06 substrate could lead to partial 0.04 loss of w a s h c o a t . Detailed 0.02 a n a l y s e s are u n d e r w a y to 0 determine the precise reason 3 5 0 I-I 340 ~ 4 0 0 7T7~ MC only for loss of conversion. The corresponding tests for 340 A Figure 18. NMHC emissions for bag 1A and total FTP ceramic preconverter are in cycle with main converter alone (config. 1) vs. main progress and their results will converter plus three different preconverters (config. 3): be reported in the near future. all converters aged for 60 hours The effect of aging on FTP emissions was also measured using exhaust configuration 3. Each of the three preconverters together with the main converter was aged for 60 hours prior to the F I ~ test. Both bag 1A and the total FTP emissions were monitored. The NMHC, CO and NO x emissions from bag 1A as well as the total FTP emissions for each of the three preconverters in series with the main converter are compared with those from main converter only (configuration 1) in Figures 18, 19 and 20. Again, it is clear from these data that the 350 O ceramic preconverter outperformed both 340 A ceramic and 400 ~ metallic preconverters due to its lower thermal mass, high surface area and uniform flow distribution. 7. SUMMARY

The primary objective of designing a ceramic preconverter system for light-off application has been met by proper selection of cordierite composition, cell geometry, substrate contour, size and volume, high temperature durable mat, and a robust packaging design. The low porosity cordierite composition, EX-22, with two unique cell geometries, is rec-

321 ommended as the substrate of 1.4 choice with inherent advan] 9Bag 1A contribution tages of c o m p a c t n e s s , low 1.2 mass, high surface area, high 1.0 strength, low thermal expansion, and high temperature ~ o.a capability. These characteristics allow the ceramic preconverter o 0.6 to meet light-off requirements o o.4 under variable operating conditions over the specified 160,000 o.2 vehicle kilometers. The triangu3 4 0 ~1 400 ~ MC only 350 0 lar cell structure provides the added benefit of in-plane isotropy with 50 to 100% high- Figure 19. CO emissions for bag 1A and total FTP cycle er biaxial compressive strength with main converter alone (config. 1) vs. main converter than that of square cell struc- plus three different preconverters (config. 3): all converters ture, which permits a more aged for 6O hours robust packaging design. .... The circular substrate contour is ideal for close-coupled o.e 9 1 7 6 1A eo,,~r,b~t,o, light-off application in that it Q Total ~ emlulons , occupies small volume, facilio.s i tates optimum flow distribu- ~ 0 . 4 tion and catalyst utilization, -. and is amenable to tourniquet ,, o . a p a c k a g i n g with u n i f o r m l y o high mounting pressure. Other z o.2 contours, e.g. biradial oval, o.1 can also be tailored for preconverter application, o The choice of special mat, 3so U 34o a 4oo rvr~ MC o n l y InteramrM 100, with built-in high temperature edge seals Figure 20. NO x emissions for bag 1A and total FTP cycle ensures high mounting pres- with main converter alone (config. 1) vs. main converter sure and e x c e l l e n t erosion plus three different preconverters (config. 3): all converters resistance required for durable aged for 60 hours p a c k a g i n g . In addition, its wide operating temperature range and superior insulation property relative to standard mats used in underbody application permit higher operating temperature while retaining bulk of the heat within the converter for efficient light-off operation and simultaneously limiting the shell temperature to acceptable values. The packaging design employing such a mat showed no degradation after 100 hours of high temperature vibration test and yielded uniformly high mounting pressure during axial push-out tests. The back pressure measurements in the chassis dynamometer test have also shown that the EX-22 ceramic preconverter is a viable candidate for light-off application. The light-off time and the heat-up rate as measured on a 4 g, 6 cylinder engine, were identical for both ceramic and metallic preconverters. The ceramic preconverter was most effective in reducing cold-start emissions during the 40-120 sec. time interval of FTP cycle. The NMHC emissions, in particular, were 55% lower after 60 hours of aging and 49% lower after

322 120 hours of aging than those from metallic preconverter indicative of greater potential of washcoat degradation in metallic preconverter. The FTP emissions test demonstrated that the 350 Q ceramic preconverter outperformed the 400 7'err metallic preconverter of identical volume after both 60 and 120 hours of aging in exhaust configurations 2 and 3. The average shell temperature for ceramic preconverter is 200~ lower than that of the mantle for metallic preconverter indicating that the former retains more exothermic heat due to mat insulation and promotes early light-off of the main converter. The metallic preconverter radiates heat to surrounding environment and is less effective in transmitting exothermic heat to the main converter. The durability, back pressure, light-off and aging d,-ita as measured in the tests described in the paper clearly demonstrate that a properly designed ceramic preconverter system is a viable and cost-effective approach to meeting TLEV and LEV emission standards. ACKNOWLEDGEMENTS

The authors acknowledge the valuable assistance of Virginia Doud and Nancy Foster of Corning's Technology Division in the preparation of this paper. They are also grateful to Mark Sickels of Arvin Automotive, Phil Weber of Southwest Research Institute, and Paul Stroom of 3M Company for providing durability, back pressure and catalyst activity data. REFERENCES

1. 2. 3. 4.

Howard, G., Automotive Visions, England; Oct. '93. Maattanen, M. and Lylykangas, R.; SAE Paper No. 900505; February, 1990. Gulati, S. T.; Reddy, K. P. and Thompson, D. F.; SAE Paper No. 902170; October, 1990. Gulati, S. T." Geisinger, K. L.; Reddy, K. P. and Thompson, D. F.; SAE Paper No. 910374; February 1991. 5. Gulati, S. T.; SAE Paper No. 850130; February, 1985. 6. Gulati, S. T.; CAPoC-2 Conference, Brussels, Belgium; September, 1990. 7. Gulati, S. T.; Ten Eyck, J. D. and Lebold, A. R.; SAE Paper No. 930161; March, 1993. 8. Gulati, S. T.; Ten Eyck, J. D. and Lebold, A. R.; SAE Paper No. 922252; October, 1992. 9. Lachman, I. M. and etal.; Ceram. Bull.; 1981. 10. Lachman, I. M. and Lewis, R. M.; "U.S. Patent 3885977;" May 27, 1975. 11. Day, J. P.; SAE Paper No. 902167" October, 1990. 12. Bagley, R. D.; "U.S. Patent 3790654;" February 5, 1974. 13. Gulati, S. T.; SAE Paper No. 881685; October, 1988. 14. Gulati, S. T.; Socha, L. S.; Then, P. M. and Stroom, P. D.; SAE Paper No. 940744; February 1994. 15. Gulati, S. T. and Reddy, K. R; SAE Paper No. 930165; March, 1993. 16. Gulati, S. T. and Reddy, K. R; SAE Paper No. 922333; October, 1992. 17. Reddy, K. R and Gulati, S. T.; SAE Paper No. 932663; October, 1993. 18. Gulati, S. T. and Sweet, R. D.; SAE Paper No. 900268; February, 1990. 19. Gulati, S. T.; Summers, J. C.; Linden, D. G. and White, J. J.; SAE Paper No. 890796; February, 1989. 20. Gulati, S. T.; Cooper, B. J.; Hawker, R N.; Douglas, J. M. and Winterborn, D.; SAE Paper No. 910372; February, 1991. 21. Gulati, S. T. and Schneider, G." ENVICERAM '88, Cologne, W. Germany; December, 1988. 22. Weibull, W." J. App. Mech., Vol. 18" 1951. 23. Gulati, S. T. and Helfinstine, J. D." SAE Paper No. 852100; October, 1985.

323 24. 25. 26. 27. 28. 29. 30.

Gulati, S. T.; SAE Paper No. 750171; February, 1975. Gulati, S. T. and Merry, R. P.; SAE Paper No. 840074; February, 1984. Stroom, R. D.; Merry, R. D. and Gulati, S. T.; SAE Paper No. 900500; February, 1990. "Series 500 Shaker;" Umholtz-Dickie Corp., Wallingford, CT. Socha, L. S. and Thompson, D. E; SAE Paper No. 920093; February, 1992. Socha, L. S.; Thompson, D. F. and Weber, P. A.; SA.E Paper No. 930383; March, 1993. Socha, L.S.; Thompson, D.F. and Weber, P.A.; SAE Paper No. 940468; February, 1994.




325

I M P R O V E M E N T OF THE T H E R M A L S T A B I L I T Y OF CERIA SUPPORT. M. Pijolata, M. Prina, M. Soustellea, O Touretb, P. Nortierb, aDdpartement de Chimie-Physique des Processus Industriels, Ecole Nationale Supdrieure des Mines, 158 cours Fauriel, 42023 Saint-Etienne Cedex (France) bSynth&e Mindrale, Centre de Recherche de Rhrne-Poulenc, 52 rue de la Haie Coq, 93308 Aubervilliers Cedex (France)

ABSTRACT The experimental variations of the rate of crystallite growth in ceria at 943 K are reported as a function of the content (_< 10 at % ) in foreign cations or additives such as Mg 2+, AI3+, y3+, and Si4+ ions. The process of surface area decrease due to crystallite growth is described by a kinetic model involving oxygen and cerium ions diffusion. From the calculation of the concentration in oxygen vacancies, electrons and cerium vacancies, the diffusion current can be obtained versus the oxygen partial pressure and the foreign cation concentration. The rate obtained from the model is compared to the experimental one.

1. INTRODUCTION

It is now well known that ceria promotes the performance of three-way catalytic converters used to remove carbon monoxide, nitrogen oxides and unburned hydrocarbons from automobile exhaust [1,2]. The high oxygen storage capacity of ceria improves the catalytic performances by acting on the composition of the gaseous mixture, storing oxygen under lean operating conditions and releasing it under rich conditions. Moreover, a great advantage of ceria as a catalytic support is that it stabilizes the dispersion of Pt particles [3]. In

326 addition, the enhancement of the catalytic activity of a Rh supported on doped ceria has been recently demonstrated [4]. For these reasons the thermal stability of ceria itself has been investigated and several patents claim that the addition of cations like aluminum, zirconium, or silicium cations improves the stability of its surface area at high temperature [5]. However a comprehensive study of the behaviour of ceria at high temperature has not yet been achieved and the role of additives on its textural stability is not clearly understood. We have done an experimental study and a modeling of the surface area decrease of ceria doped with several cations (Mg2+, y3+, A13+and Si4+) at 943 K. This temperature has been chosen in order to allow a kinetic study, but it is rather low for a catalytic application. To ascertain the results in practical conditions, we have verified the stabilizing effect of the most promising cations at higher temperatures such as 1073 and 1173 K.

2. EXPERIMENTAL PROCEDURE

HSA ceria powder (135 m2g-1) was supplied by Rhrne-Poulenc. The major impurities were La 3+ ions (0.15 at %). In previous studies [6,7] we have shown that the surface area results from the contribution of a microporous surface and an external surface area. During thermal treatment at 943 K the surface area decreased, and after only two hours there was no longer any microporous surface. For this reason, we have chosen to follow the decrease of the external surface area by looking at the mean diameter of ceria crystallites. The amplitudes of the variations of the mean crystallite diameter of ceria are therefore a good indication of its thermal stability. The mean crystallite diameter was obtained from the line broadening of the X-ray diffraction (XRD) pattern and using Warren's formula [7]. In the initial sample it was equal to 13.7 ran, then it increased up to 20 nm after five hours at 943K. This variation was found to be in agreement with observed decrease of the external surface area from 63 to 30 m2g -1 . Foreign cations were added to the powder according to the incipient wetness method from nitrate salts for Mg2+, y3+, and A13+, and from tetraethyl ammonium silicate for Si4+. A subsequent washing with water was achieved in order to eliminate nitrates from the powder surface. The residual concentration in nitrates was lower than 0.015 at %. The samples were then calcined at 723 K in the ambiant air for four hours. Final concentrations of the foreign cations added were fixed equal to 0.5, 1.0, 2.0 and 10.0 at %.

327

v

y3+

a00

A! 3+

400

300

300

200-

200 '

I00

100 . 2

.

.

. 6

4

v

.

~

8

0

10

0

a(%)

,

|

2

4

8

10

a(%)

v

400

Mg

2+

300

200-)

200

I00

100 I ~

2

|

|

I

I

4

Si 4+

a00

300

0

(A/h)

~

6

8

10

a(%)

0

2

4

6

8

10

a(%)

Figure 1" Experimental variations o f the rate o f crystallite size increase in doped ceria at 943 K, with P 0 2 - 13.33 kPa (---) and 0.13 kPa (~), versus the additive concentration a (at %). The star corresponds to undoped ceria.

321~ The samples were characterized by various methods (ESCA, 27A1 NMR, STEM, XRD) to verify the formation of a solid solution. The detailed results are not reported in this paper, but can be found in reference [7]. The doped (and undoped) samples were calcined at 943 K in a Pyrox B80 furnace under a flowing mixture of helium, oxygen and water vapor. The oxygen partial pressure varied from 0.2 to 30 kPa, and the water vapor partial pressure varied from 0.1 to 3.3 kPa. In order to avoid reproducibility errors, all the samples (undoped and doped with the same content) were calcined simultaneously. The experimental curves of the mean crystallite diameter (D) versus time (t) of calcination were fitted by a mathematical function in order to calculate the experimental rate dD/dt. As previously explained [6,7], the variations of dD/dt, at a fixed value of D (14 nm in this study), were then obtained versus the oxygen partial pressure. No influence of water vapour was observed in the investigated range of pressure.

3. EXPERIMENTAL RESULTS

Figure 1 shows the experimental variations of the rate of crystallite size increase in doped eeria versus the foreign cation concentration. The figure displays two sets of results: continuous lines corresponding to an oxygen partial pressure of 0.13 kPa and dotted lines corresponding to an oxygen partial pressure of 13.33 kPa. For comparison the rate measured without additive addition (about 200 A.h -1) has been reported in the figure. Figure 1 shows that the rate is strongly influenced by the addition of the foreign cation.

4. MODELING The crystallite growth process occurs through an atomic transport at high temperature whenever two particles are in contact with each other, due to a concentration gradient which itself results from a curvature radius gradient: in the following "R>0" refers to surface areas of CeO2 particles having a positive curvature radius, and "R 0" surfaces :

-o~ 1 +~ 2

>o

+2C

o,

~>o

=% x

>o

x

+2Cecea

0

>

(1)

2. Oxygen vacancy diffusion (and electron diffusion ) :

~O~o-~ ~O~,o (o;~ -~ OLo) and %~o -~ c% >0

>0

(2)

3. Vacancy creation at "R < 0" surfaces :

o~ +o~

....

1~0 l" Prm--fkPa 1

=

L

=

L

I

=

60

d

~0 1

OI

o

p=88 '

'

'~o

'

t. , S

'8oo'

~12'00

~/

J

I

/ 30 I-

/

/,_/

II

0 0

I

g.

:

L

I

Po,,

=v

~

I

,

--1

o

"

"=

I

.:znzo

-,-600 =x~," 0 I

,;-~ooo=-,o, i

:

,

4

§

;

: '

'

I

' ' § 1400 m'r

' '

t/'~..~i

t

i

,

i

//_~ ,7/" _.,

.

l

I

I ,,

//.//'

I I .43o

II

i

/

Jl

''

/7

/

OE

,/~I, ,,7"~/i ,

T=350"C

~:

.

2

kPa

I

,

3

-~0 4

Fig 7 A galvanostatic transient during Fig. 8 Effect of Po2 and catalyst C2H4 oxidation on Rh catalyst, potential on the rate of C2H4 oxidation T=350~ Poz = 2 kPa, PC2H4=5.5kPa on Rh.

SiO2, y-m1203, ZrO2(8%Y203), TiO2(4%WO0. Since the NEMCA effect is due to the change in catalyst work function eF with changing catalyst potential (Ae@=eAVwR) [16,18] and to the concomitant back-spillover of promoting oxide ions onto the catalyst surface [16,28], it is likely flint the above catalyst support sequence corresponds to increasing work ftmction of the supported Rh crystallites, i.e. e@ is lowest for Rh supported on TiO2 and highest for Rh supported on TiO2(4%WO0.

384 4.CONCLUSIONS

It was found that the catalytic activity of three-way catalysts can be altered significantly by using different supports for each noble metal component. This may be due to electronic interactions between the metal and the support [9,10] and/or due to oxygen back spillover from the supports to the catalyst as in the NEMCA experiments [ 16-18,28 ]. The following sequence of catalytic activity was observed, with minor variations for each reaction: Rh: TIO2(4% WO3)>ZrO2 (8% Y203)> 7-A1203, SiO2>TiO2 Pd: ZRO2(8% YzO3)> 7-AlzO3>TiOz(4% WO3), SiO2>TiO2 Pt: SiOz>ZrOz(8% Y203), ~'-A1203>TiOz>TiOz(4% WO3) Qualitatively similar results were obtained in the NEMCA study of CzH4 oxidation. It was shown that the catalytic rates and also the location of the abrupt break in the rate vs Poz curves (most likely corresponding to the formation of a surface oxide) can be adjusted by means of the externally applied potential. The observed strong similarities between the NEMCA effect [ 16-18] and the effect of dopant-induced-metal-support interactions [6,7,9,10] suggests that the origin of both effects may be similar. Surface spectroscopic and work function measurements could further elucidate this point.

REFERENCES

Schwab, G-M., in "Advances in Catalysis", Vol. 27, p. 1, Academic Press, Orlando, FL, 1978 Solymosi, F., Catal. Rev., 1 (1967) 233 Tauster, S.J., and Fung, S.C., J. Catal., 55 (1978) 29 Ko, C.S., and Gorte, R.J., J. Catal., 90 (1984) 59 Sadeghi, H.R., and Henrich, V.E., J. Catal., 109 (1988) 1 Akubuiro, E.C., and Verykios, X.E., J. Catal., 103 (1987) 320 Akubuiro, E.C., and Verykios, X.E., J. Catal., 113 (1988) 106 Solymosi, F., Tombacz, I., and Koszta, J., J. Catal., 95 (1985) 578 Ioannides, T., and Verykios, X.E., J. Catal., 140 (1993) 353; 143 (1993) 175; 145 (1994) 479 10 Ioannides, T., Verykios, X.E., Tsapatsis, M., and Economou, C., J. Catal., 145 (1994)491 11 Vannice, M.A., Twu, C.G., and Moon, S.H., J. Catal., 79 (1983) 70

385 12 Metealfe, I.S., and Sundaresan, S., AIChE Journal, Vol. 34(6) (1988) 1048 13 Oh, S.H., J. Catal., 124 (1990) 477 14 Yao, H.C., Stepien, H.K., and Gandhi, H.S., J. Catal., 61 (1980) 547 15 Kummer, J.T., J. Phys. Chem., 90 (1986) 4747 16 Vayenas, C.G., Bebelis, S., Yentekakis, I.V., and Lintz, H.-G., Catalysis Today, 11 (1992) 303-442 17 Yentekakis, I.V., Moggridge, G., C.G. Vayenas, and R.M. Lambert, J. Catal., 146 (1994) 292 18 Vayenas, C.G., Bebelis, S., and Ladas, S., Nature (London), 343 (1990) 625 19 Engel, J., and Ertl, G., in "Advance in Catalysis", Vol. 28 (1979) 1-78 20 Creighton, J., Tseng, F., White, J., and Tumer, J., J. Phys. Chem., 85 (1981 ) 703 21 Kobylinski, T.P., and Taylor, B.W., J. Catal., 33 (1974) 376 22 Pliangos, C.A., Yentekakis, I.V., and Vayenas, C.G., J. Catal. (1994) submitted 23 Gordonna, G.W., Kosanovich, M., and Becker, E.R., Platinum Metals Rev., 33(2) (1989) 46 24 Hammerle, R.H., and Truex, T.J., S.A.E. Paper, No 760090 (1976) 25 McCabe, R.W., and Wong, C., J. Catal., 121 (1990) 422 26 Kirn, Y., Schreiffels, J.A., and White, J.M., Surf. Sci., 114 (1982) 349 27 Hegedus, L.L., and Gumbleton, J.J., Chemtech, 10 (1980) 630 28 Ladas, S., Kennou, S., Bebelis, S., and Vayenas, C.G., J. Phys. Chem., 97(35) (1993) 8845


A. Frermet and J.-M. Bastin (Eds.) Catalysis attd Automotive Pollution Control Ill

Studies in Surface Science and Catalysis, Vol. 96 1995 Elsevier Science B.V.

387

SYNTHESIS AND STUDY OF HONEYCOMB MONOLITHIC CATALYSTS FOR CATALYTIC COMBUSTION Z.R.Ismagilov, G.V.Chernykh, R.A.Shkrabina. Boreskov Institute of catalysis, 5 Prospekt Ak. Lavrentieva, 630090 Novosibirsk 90, Russia

ABSTRACT This paper concerns the synthesis of catalysts able to retain their high activity upon the catalytic combustion of hydrocarbons at temperatures up to 1100~ SiO 2, La203, CeO 2 additives are used to privent alumina washcoat on cordierite monoliths from sintering. Catalysts containing Pt and Pd have been investigated. The catalysts with Pd on AI203+SiO 2 support have been found to be most active and stable at high temperature.

1.1NTRODUCTION

Catalytic combustion as an alternative to conventional thermal combustion received considerable attention in the past decade [1-3]. It is known that the catalysts for high temperature combustion should possess the following properties: high catalytic activity; developed geometrical surface, low pressure drop, high thermal stability and high specific suface area of the support; thermal stability of the active component and support under a long term catalyst operation at high temperatures. Typically, monoliths made of various materials are used for supporting such catalysts [4]. A thin oxide layer (usually ~/-A1203) coveting the walls of monolith channels provides a high specific surface area. At high temperatures a phase transformation of 7-A1203 to ot-A1203 occurs decreasing surface area resulting in catalyst activity reduction. Various additives such as La203, CeO2,

388

ZrO2, BaO, etc. introduced into alumina were found to increase its thermal activity [6,7]. Catalysts containing noble metals are known to be the most active catalysts for the complete combustion of hydrocarbons [8]. During the catalyst operation at temperatures higher than 800~ the active component starts to sinter and evaporate. Therefore, the active component should have a low vapour pressure, or it should be strongly bonded to the thermally stable support [9]. Pt and Pd are the most often used noble metals. A better thermal stability performance of the Pd/A120 3 system is explained by a strong interaction of PdO with A120 3 surface. PtO interacts with alumina less strongly, therefore, Pt/AI20 3 system undergoes considerable sintering in air at temperatures exceeding 600~ [10]. PdO formation as well as the sintering of Pt particules decreases the catalyst activity. Thus, the problem of catalyst desing can be divided into several subproblems: 1. synthesis of a thermally stable support including monolith washcoating with oxides, selection of modifying additives and their introduction into the oxide layer; 2. catalyst synthesis: deposition of the active component and the selection of their chemical composition improving its thermal stability.

2.EXPERIMENTAL

Cordierite monoliths 10xl0xl0mm wer used as the catalyst support. Its properties are listed in Table 1:

Table 1 Properties of monolith Parameters Cell size, mm Number of cells per cm 2 Wall thickness, mm SBET,m2/g Total pore volume, cm3/g Average pore radius (r), mkm rl,mkm r2,mkm

Value 1.2x 1.2 49 0.2 0.1 0.819 36.7 1.43 71.90

389 BET surface area was measured by argon thermal desorption. The pore structure was determined by the mercury intrusion porosimetry method (Porosizer-2300). Disperse suspensions prepared by mixing alumina hydroxide with pseudoboehmite stugture, HNO 3 and H20 have been used for washcoating. La20 3 was introduced into the suspension from La(NO3) 3 6H20, SiO2- from silica sol, CeO 2 from Ce(NO3) 6H20. cordierite monoliths were immersed in suspension for 5 min and, after being blown with air, dried at 60-80~ for 2h. to obtain high surface area of washcoat the impregnation was repeated twice, before the second immersion the monoliths were heated at 300~ for 2h. To study the properties of the support with washcoat, the monoliths (after last impregnation and drying at 60-80~ were calcined at 550~ and 1100~ for 3h.to avoid washcoat pore closure and burying of active components at high temperatures the support calcined at 1100~ was used for catalyst preparation. Pt and Pd were deposited from the aqueous solutions of H2PtC16 and H2PdC14via impregnation in excess solution followed by drying at 60-80~ THE catalysts were calcined at 600~ and 1100~ the content of the active component and additives was determined by X-ray fluorescence (VRA-20). Catalytic activity was studied using a flow-circulation technique and characterized by the rate of complete butane oxidation (W) at 5000C and a stationary butane concentration of 0.2vo1.%. The inlet reaction mixture contained 0.5vo1.% of C4H10, balance air. Pt and Pd dispersion in the samples was determined by SAXS (KRM-1 chamber)using CuKot radiation, voltage 30 kV and filament current 20 mA. The distribution of additives and noble metals over the oxide film was studied using X-ray microprobes.

3.RESULTS The data on washcoat preparation and thermal stability of the support are summarized in Table 2. The additive efficiency was defined as the ratio: I( = SBET(1100~176176 From this data it is evident that the introduction of additives allows the support surface area to increase considerably after high temperature treatement. It is well known that the additives differ in the mechanism of their interaction with alumina, but as seen from Table 2, the efficiency values of CeO2,SiO2 and La203 are rather close to each other. If the additive stabilizing effect is estimated as a

390 ratio between SBET of pure alumina and that of doped alumina at 1100~

the

following series of additive efficiency can be obtained: SiO2~CeO2>La203. This series is in good agreement with the reference data. Based on the results obtained and on the assumption that CeO2 can be stabilize the active components (Pt and Pd) as well, the supports modified with this additive and SiO 2 were chosen for the catalyst preparation. As seen from Table 3 the catalysts calcined at 600~ and deposited on a support containing 5wt.% of CeO2 are more active independently of the content and composition of the active component. The increased palladium loading leads to the catalyst activity enhancement for both supports

Table 2 Properties of washcoat and support thermal stability K N~ Washeoat A1203 SBET,m2/g

3

A1203 A1203 + 5% CeO2 A1203+ 2% SiO2

4.

A1203 + 2% La203

1 2

wt.% 8.1

550~ 25.0

1100~ 0.7

9.1

24.0

9.1

0.03 0.38

9.7

25.0

9.2

0.37

9.4

.23.9

8.3

0.35

Table 3 Activity of catalysts for C4HI 0 oxidation N~

Washcoat

1 2 3 4 5 6

AI203 + 5% CeO2 . . . . . . A1203 + 2% SiO2 . . . . . . . . . . . .

Pt, wt.% Pd,wt.% W. 102,C4Hlo/gs 600~ 1100~ 5.6 0.2 -7.1 0.2 12.6 3.0 0.2

-0.2 0.5

9.1 10.7 11.7

2.6 10.7 10.7

For samples treated at 1100~ the following results were obtained. All catalysts on A1203 + CeO2 support lose their activity. The samples containing 0.2wt.% of Pd (samples 2,3) are deactivated the most, and that containing 0.2wt.% ofPT (sample 1) - the least. Pd/A1203 + SiO2samples retain their high activity (samples 5,6).

391 in order to explain the effects observed, a more detailed study of supported samples eotaining CeO2 additive was performed. All samples were shown by SAXS to be polydispersed and to contain particules ranging from 50A to 180A in size. But no strong relationship between the active component particule size, the calcination temperature and the catalyst composition was observed. With increasing temperature to 1100~ polydispersive distribution is retained and the average size of active component partieules tends to slightly increase. For some mnples, motly with palladium, calcination at 1100~ leads tothe shift of SAXS particule size distribution curves to the interval 20-40 A. This formal increase of dispersion under calcination in air can be explained by significant growth of an oxide layer over sintered metal particules with simultaneous formation of an interphase boundary with the washeoat, thus, the metal particule size, observed by SAXS, is smaller. It should be noted that due to the complexity of the catalyst studied, care must be taken in the interpretation of dispersion measurements made by SAXS. It was found by X-ray microprobes (samples 1-3 ) that the thickness of the washcoat cover is around 50 mkm. CeO2,PtandPd are distributed uniformaly with respect to A120 3 in the samples calcined at 600~ Calcined at 1100~ leads to noticeable redistribution of active components: platinum in the catalyst Pt/A120 3 + CeO 2 concentrates on the outer surface of the monolith wall to a higher extent than palladium inPd/A120 3 + CeO2 4.CONCLUSIONS The main findings of this work call be summarised as follows. The introduction of CeO2 , SiOzstabilizes the support surface area at high temperatures. The catalysts prepared on the thermally stable supports containing Pd on A120 3 + SiO 2 retain their high activity after treatement at 1100~

392 REFERENCES

10

R. Prasad, L. A. Kennedy and E. Ruckenstein, Cat. Rev.-Sci. Eng., 26(1),1-58(1984) H. Arai and M. Machida, Catal Today, 10, 81-94 (1991). Z. R. Ismagilov and M.A. Kerzhentsev, Catal. Rev.-Sci. Eng., 32(1-2), 51-103(1990) D.L. Trimm, Appl. Catal., 7,249-282(1983). B.Beguin, E. Garbowski and M. Primet, J.Catal., 127, 595-604(1991). M. Machida, K. Eguchi and H. Arai,J. Catal., 103,385-393(1987). M. Machida, K. Eguchi and H. Arai J; Catal., 120,377-386(1989). Y. Morooka and A. Ozaki, J. Catal., 5, 116-124(1966). M. F. M. Zwinkels, S.G. Jaras and P.G. Menon, Catal Rev.-Sci. Eng., 35(3), 319-358(1993). M. A. Leeand E. Ruckenstein, Catal Rev.-Sci. Eng.,25,475-550(1983)

A. Frennet and J.-M. Bastin (Eds.) Catalysis and Automotive Pollution Control 111


393

S T R U C T U R E AND C A T A L Y T I C A C T I V I T Y OF MIXED OXIDES OF P E R O V S K I T E S T R U C T U R E V. Mathieu - Deremincel, J.B. Nagy and J.J. Verbist Groupe de Chimie Physique, Facultds Universitaires Notre-Dame de la Paix, 61 Rue de Bruxelles, B-5000 Namur, Belgium

ABSTRACT The Lal-xCexBO3 (B = Ti, Cr, Mn, Fe, Ni, Co) mixed oxides of perovskite structure present a catalytic activity for CO oxidation and NO reduction which increases with increasing Ce content. LaCoO3 and LaMnO3 are the more active compounds for both CO oxidation and NO reduction. The oxidation of CO by 02 follows a suprafacial type mechanism where the adsorbed oxygen is the active species. The reduction of NO by CO is best explained by a redox mechanism. Ce is only incorporated in a limited amount in the perovskite structure and a concomitant formation of CeO2 is also observed. For a low Ce content, CeO2 is highly dispersed on the surface of the catalyst particles, while larger particles are obtained at higher Ce content. The presence of Ce leads to an increase in both CO oxidation and NO reduction activities. The CO oxidation is dependent on the dispersion of CeO2 on the mixed oxides particles. On the other hand, the NO reduction does depend on the Ce content in the perovskite structure.

1. INTRODUCTION

Despite the fact that perovskite-type oxides have been suggested as substitutes for noble metals in automotive exhaust catalysis [1], relatively few studies were devoted to the synthesis, characterization and catalytic activity of these catalysts. These compounds, of general formula ABO3, generally include a lanthanide element A and a transition metal B. Partial substitution of A by Ce is also interesting, as Ce is a well known additive of exhaust catalyst [2]. Its oxygen storage ability is used to broaden the air/fuel ratio window, improving the activity of three way catalysts (CO, hydrocarbon oxidation, NO reduction). 1 Present address : Solvay & Cie, Rue de Ransbeek 310, B-1120 Bruxelles, Belgium

394 It seems that the lattice oxygen plays a direct role in the oxidation of CO. Indeed, it was found that the catalytic activity is maximum, if the bond energy of the lattice oxygen is minimum [3]. Hence, the oxygen vacancy is also an important factor for the catalytic activity. The partial substitution of the A element can monitor the oxygen vacancy. If Ce(IV) is introduced in the perovskite structure A site vacancies are produced [4]. The partial substitution of B element by Pt (IV) increases greatly the CO oxidation activity of Lao.7Pbo.3MnO3 perovskite [5]. For the NO reduction by CO AMnO3 perovskites were the most studied catalysts [6]. The importance of anion vacancies was emphasized for the good catalytic activity. The ACoO3 was also found a good candidate for both CO + 02 and CO + NO reactions [7]. Very recently perovskite-related oxides were also proposed as catalysts for the direct decomposition of NO into N2 and 02 [8, 9]. This paper deals with the characterization and catalytic activity of cerium substituted lanthanum perovskites Lal-xCexBO3 (B = Ti, Cr, Mn, Fe, Ni, Co),x ,varying from 0 to 0.6 [10].

2. EXPERIMENTAL

Lal_xCexBO3 compounds were synthesized by evaporation of a solution of the respective metal nitrates or oxalates and calcination of the precursors either at 1000~ or at 1200~ for 5 h [11]. X-ray powder diffraction patterns were recorded on a Philips PW 1730 diffractometer using Ni filtered Cu Ka radiation. XPS spectra were obtained on a Hewlett Packard 5950 A spectrometer with A1 Ka radiation. The catalysts were tested for the CO + 02 and CO + NO reactions in a flow reactor system. Before the tests, the compounds (1.0 g) mixed with small glass beads (weight ratio 1:1) were pretreated overnight in N2 at 400~ and then in a mixture of CO, 02, N2 and Ar or CO, NO, N2, Ar, respectively for 30 min at the same temperature to attain steady- state conversion. The same flow rate (Q = 150 ml/min), the same mixture of reagents (20 % CO, 10% 02, 70 % N2 or 20% CO, 20% NO, 20% Ar, 40% N2, respectively, in mol %) and the same reaction temperature (T = 100-400~ or 300-500~ respectively) were used to compare the activity of the different catalysts. For the determination of the kinetic schemes, the differential mode of the reactor was used (% conversion < 15%).

395 3. R E S U L T S AND DISCUSSION 3.1. X-ray Diffraction

Since no traces of La2 03 or BOx appear in the diffraction patterns of LaBO3 (B = Cr, Mn, Fe, Co), the perovskite is completely formed at 1000~ in the systems not containing Ce. With B = Ni or Ti, additional phases appear which are La2 NiO4 or La2 Ti2 07, respectively. Moreover, the stoechiometry of the latter perovskite is Lao.7TiO3. The Ce introduced in the reagents is not totally incorporated in the perovskite lattice. The excess crystallizes as CeO2 [4, 12]. The latter is influenced by the nature of metal B (Table 1). For compositions x < 0,05, no trace of CeO2 is detected. This can be due either to a total incorporation of Ce into the perovskite lattice or to a very highly dispersed (and/or amorphous) CeO2 not detected by XRD. For higher Ce content, the relative intensity of CeO2 increases with increasing x, the slope being in the following order as a function of B : Ni > Co > Mn > Cr > Fe > Ti.

Table 1 Relative heights of X-ray diffraction peaks characterizing the different catalysts calcined at 1000~ ICeO2 flLaBO3

a

a

xb

Ti

Cr

Mn

Fe

Co

Ni

0.01 0.03 0.05 0.07 0.10 0.15 0.20 0.40 0.60

-

-

-

0

0

0 0 0.05 0.13 -

0 0.06 0.22 0.73 -

0 0.06 0.14 0.31 0.77 1.37

0 0.04 0.08 0.08 0.17 0.21 0.46 0.98

0 0.12 0.17 0.22 0.26 0.35 0.88 1.41

0 0 0.13 0.21 0.33 0.28 0 58 1 20 1 79

ICeO2-d=3.16A;ILao.7TiO3-d=2.74A;ILaCrO3 - d = 2.74 A; ILaMnO3 - d = 2.72 A; ILaFeO3 - d - 2.78 A; ILaCoO3 - d = 2.67 A; ILaNiO3 - d = 2.74 A b :x is defined as Lal_xCexBO3

396

Table 2 Amount of adsorbed oxygen (in %) and Olattice/La atomic ratios of perovskites calcined at 1000~ Perovskites

Oads (%)

Olattice/La a

La0.7TiO3 LaCrO3 LaMnO3 LaFeO3 LaCoO3 LaNiO3

35.9 42.5 49.2 61.9 84.9 71.0

4.67 3.04 2.53 1.75 0.59 1.09

a : Theoretical atomic ratios : 3.0, except for Ti(4.3) The formation of extra perovskite lattice CeO2 gives rise to three different results: - appearance of A vacancy sites (O) following Lal-xOxBO3 +xCeO2, - migration of (excess) B ions outside the perovskite lattice to yield BOx : Lal-xB 1-xO3-x + xBOx + xCeO2. - the occurrence of both phenomena. For low Ce content, the first process is predominant, while for higher Ce content BOx phase also appears. The relative importance of the two processes is highly dependent on the nature of B. Neither TiO2 nor Cr203 are detected for any initial x value. Only traces of Fe203 are shown for x = 0.40 and 0.60. Mn203 starts to appear for x = 0.20 and CoO for x = 0.10. NiO is detected for any x values studied. 3.2. X - r a y p h o t o e l e c t r o n s p e c t r o s c o p y

The valence state of La and B ions in LaBO3 perovskites is equal to (III) in all compounds without Ce, but for Ti, where Ti is in (IV) oxidation state, in agreement with the stoechiometry ofLao.7TiO3 perovskite. The atomic ratio computed form the B2p and La3d core peak intensities is close to the theoretical value of 1 in LaBO3 for B=Cr, Mn, Fe and Co. For Ti, this ratio is equal to 1.44, corresponding to the above mentioned stoechiometry. The XPS spectra of O ls are more interesting to characterize the nonstoechiometric composition of the perovskites. Indeed, their catalytic activity is

397 dependent on the excess or default of oxygen in the lattice. The higher energy O ls peak (Eb = 530.5 eV with respect to Eb of carbon, 284.7 eV) is attributed to adsorbed oxygen and the lower energy peak (Eb = 529.0 eV) to lattice oxygen [13]. The amount of adsorbed oxygen increases as a function of the atomic number of B ions, exception for Ni (Table 2). From the comparison of the theoretical OlatticefLa ratio (equal to 3) with the experimental values, oxygen deficiency is detected for all B ions, excepting Ti and Cr (Table 2). The importance of oxygen deficiency increases with the atomic number of B ions. Hence, it seems that the oxygen is essentially adsorbed at anion vacancies. The perovskites synthesized in presence of Ce do not exhibit any bond energy difference for La or B ions. On the oflaer hand, despite of the complexity of the Ce XPS spectra, the Ce3d core peak intensities and the Ce(IV) satellite intensity allowed us to estimate the relative amotmt of Ce(III) and Ce(IV) on the surface [10,11]. The amount of Ce(III) is considered as being incorporated in the perovskite lattice, Ce(III) replacing La(III) in Lal-xCexBO3. For x Fe > Mn > Co > Cr. A rather high amount of Ce(III) accompanies Ti, while it is difficult to incorporate it in presence of Cr. Fe, Mn and Co represent intermediate cases. 100 80

9 9 o 9

o

60 ~,

Ti Cr Mn Fe Co

40

l 0.0

.,, 0.1

0.2

0.3

0.4

0.5

0.6

Figure 1. Variation of the amount of Ce(llI) (in %) as a function of x in the perovskites Lal-xCexB03.

398

Table 3 Atomic ratios Ce/La from XPS La3d and Ce3d peak intensities for the catalysts Lal_xCexB03 calcined at 1000~ Ce/La (XPS) x

Ce/La (synthesis)

Ti

Cr

Mn

Fe

Co

0.03 0.05 0.07 0.10 0.15 0.20 0.40 0.60

0.031 0.052 0.075 0.11 0.18 0.25 0.67 1.50

0.12 0.23 0.45 -

0.12 0.23 0.36 0.79 -

0.20 0.25 0.23 0.28 0.51 0.56 1.15

0.22 0.21 0.30 0.25 0.23 0.56 0.68 0.90

0.13 0.19 0.17 0.28 0.43 0.54 0.89

Following these values, two behaviours can clearly be distinguished. For x ~ 0.40, the surface atomic ratios are higher than the bulk values for all B ions, showing a surface excess Ce. Oppositely, for x > 0.40, due to the sintering of CeO2 particles, the surface atomic ratios are lower than the corresponding bulk values. For low x values, the surface CeO2 is highly dispersed and not detected by XRD (Table 1). For high x values, the sintering of CeO2 particles is also confirmed by XRD. Note, that the surface Ce(III)/La values are generally independent on the Ce/La ratio in the synthesis mixture. This amount of Ce is considered being incorporated in the perovskite lattice. As a conclusion, it can be underlined that Ce(III) is incorporated in the lattice, while CeO2 is either in a highly dispersed form or is found as larger particles. The O 1 s bond energies are not influenced by the Ce substitution. Two types of oxygens - lattice and adsorbed - are also distinguished as for the pure perovskites. However, the quantitative analysis is more difficult in this case, because both perovskite and CeO2 contain the two types of oxygen. The Olattice/La ratios are all smaller than the corresponding theoretical values, indicating that all the catalysts are oxygen deficient. For Fe, Co and Ni, the decrease of Oads as a fimction of x shows the same variation as Ce(III) surface (Figure 2a). Hence, it can be concluded that the

399 incorporation of Ce(III) in the lattice has a negative effect on the adsorption of oxygen. 100t 80

O Fe *

.

o Cr

Co

Mn i

40 20

rn

[

0.0

,

r

0.2

,

I

0.4

9

9 ~

!

,

~

0.60.0

r

1

0.2

~

I

0.4

0.6

X

Figure 2. Variation of the amount of adsorbed oxygen (in %) as a function of x in the perovskites Lal-xCexB03. For Cr and Mn, a continuous decrease of Oads is observed, while for Ti, Oads increases greatly as a function of x (Figure 2b). The latter could be explained by the non-stoechiometry of the initial perovskite Lao.7TiO3, by the high dispersion of the CeO2 formed which also contribute to the amount of Oads. 3.3. Catalytic activity The pure perovskites are all more active for CO + O2 than CO + NO reactions. The best catalysts for both reactions are LaMnO3 and LaCoO3. The activity of the different pervoskites for CO oxydation can be linked semiquantitatively with the ease of anionic vacancy formation in the lattice, described by the B-O bond energy (Figure 3). The formal kinetics were determined only on the less active LaCrO3 catalyst. The Langmuir-Hinshelwood model explains quite well the experimental rate equation 0.5 R=kPcoPo 2

400

I00

120

Q) o

N

"-.

I00

j\

0

90

~-

80 -

o

9

60 80

O

m

40 20

I

I ,,,

Ti

!

,I

Cr

Mn

I

Fe

~

Co

I

-

70

Ni

Figure 3. Comparison between the catalytic activity and the B-O bond energy in the perovskites LAB03 ~ = 77, Cr, Mn, Fe, Co, Ni). No CO conversion was observed in absence of adsorbed oxygen, confirming the reaction mechanism involving both adsorbed species. The apparent energy of activation is equal to 12.2 kcal mo1-1. The CO + NO reaction is better explained by a redox mechanism, where CO is oxidized by the catalyst which is regenerated by the reduction of NO. Moreover, a dissociative adsorption of NO better explains the experimental results on LaCoO3 and LaMnO3, while a molecular adsorption has to be supposed on LaCrO3 adn LaFeO3. Simultaneous adsorption of CO and NO shows a competiton for the same active sites [14]. The latter are generally surface oxygens leading to the formation of nitrates, nitrosyls, dinitrosyls, and carbonates, carbonyls, respectively. On the other hand, the dissociative adsorption of NO leads to the formation of N2 at higher temperature. The following reaction scheme is adequate for the LaCoO3 and LaMnO3 catalysts: CO + *

r

CO--*

(I)

N O + 2"

0.05 due to the formation of CeO2 on the surface. Finally the Lal-xCexNiO3 catalysts are more active than LaNiO3 for x > 0.2. For lower x values the influence of Ce is negligible. CeO2 is a relatively good catalyst for NO + CO reaction. Its activity (equal to 10 mol% CO conversion at 300~ is higher than those of Ti, Cr, Mn, Fe and Ni perovskites (1.7 %, 2.5 %, 9.0 %, 5.9 % and 2 . 1 % , respectively). Only Co perovskite shows a higher activity (equal to 40.8 % conversion). Note, that the activities are always lower for the NO reduction than the CO oxidation. For all perovskites the increase in activity as a function of x can be linked to the increase of Ce(III) content in the lattice. For Ti and Ni perovskites, after an initial increase of the activity a plateau is reached. For Fe and Cr perovskites, the activity is decreasing after the initial increase, showing a maximum in the activity vs x curves. The Mn perovskite shows an initial small decrease of activity followed by a larger increase as a function of x. The behaviour of Lal-xCexCoO3 perovskites is more complex. A quite large initial decrease of activity is observed for x < 0.05. After that value a maximum is reached at x = 0.20 (activity = 65 mol % CO conversion at 300~ followed by a decrease in activity (ca 40 mol% CO conversion at x = 0.60). For the initial addition of Ce, the activity decreases because the CeO2 fonned has a lower activity. At higher Ce content, larger CeO2 crystallites are formed freeing the more active surface of the perovskite catalyst. Finally, the activity decreases because the amount of Ce(III) incorporated in the lattice decreases. Note, that for small x values, the influence of Ce(III) concentration is hidden by the effect of CeO2 on the surface. A kinetic study for the CO + NO reaction on La0.95Ceo.05CoO3 revealed a decrease of the partial order with respect to NO : it is equal to 0.2, in comparison with the value of 0.5 obtained for the pure perovskite. Further studies are necessary to ascertain the specific role of both Ce(IV) and Ce(III) ions in the CO + NO reaction.

404 4. CONCLUSION

Ce(m-) is incorporated in the perovskite lattice for low x values in Lal-xCexBO3 perovskites.The remaining Ce is in a highly dispersed CeO2 form. For higher x values, larger CeO2 crystals are formed. The different phases formed are active in both CO + 02 and CO + NO reactions. The activity for the former reactions is always higher than that for CO + NO. The best perovskites are obtained with B = Mn and Co. REFERENCES

9

10 11 12 13 14 15 16

W.F. Libby, Science, 171 (1971) 499. F. Le Normant, P. Bernhardt, L. Hilaire, K. Kili, G. Krill and G. Maire, Stud. Surf. Sci. Catal., 30 (1987) 221. T. Shimizu, Chem. Lett., (1980) 1. T. Nitadori, S. Kurihara and M. Misono, J. Catal., 98 (1986) 221. D.W. Jolmson, P.K. Gallagher, G.M. Wertheim and E.M. Vogel, J. Catal., 48 (1977) 87. R.J.H. Voorhoeve, J.P. Rameika, L.E. Trimble, A.S. Cooper, F.S. Disalvo and P.K. Gallagher, J. Solid State Chem., 14 (1975) 395. G.L. Bauerle, N.T. Thomas and K. Nobe, Chem. Eng. J., 4 (1972) 199. Y. Teraoka, T. Harada, H. Fund~awa and S. Kagawa, Guczi L. et al. (eds), New Frontiers in Catalysis, Stud. Surf. Sci. Catal., 75 (1993) 2649. H. Shimada, S. Miyama and H. Kuroda, Chem. Lett. (1990) 1. V. Deremince-Mathieu, H. Collette, J.B. Nagy, E.G. Derouane and J.J. Verbist, Inorg. Chim. Acta, 140 (1987) 41. V. Deremince-Mathieu, PhD Thesis, FUNDP, Namur, 1989. H. Arai, T. Yamada, K. Eguchi and T. Seyiama, Appl. Catal., 26 (1986) 265. J.L.G. Fierro and L.G. Tejuca, Appl. Surf. Sci., 27 (1987) 453. see e.g.M.A. Pefia, J.M.D. Tascon, J.L.G. Fierro and L. Gonzalez Tejuca, J. Colloid Interface Sci., 119 (1987) 100 and references therein. J.M.D. Tascon and L.G. Tejuca, React. Kinet. Catal. Lett., 15 (1980) 185. R.J.H. Voorhoeve, in 'The Catalytic Chemistry of Nitrogen Oxides', J.C. Larson, ed., New York, 1975, p 215.

A. Frennet and J.-M. Bastin (Eds.)

Catalysisand AutomotivePollutionControl111


405

PREPARATION OF ALUMINA SUPPORTED CERIA. I : SELECTIVE M E A S U R E M E N T OF THE SURFACE AREA OF CERIA AND FREE ALUMINA. R. Fr6tya, P. J. L6vya, V. Perrichona, V. Pitchona, M. Primeta, E. Rogemonda, N. Essayema, M. Chevrierb, C. Gauthierb and F. Mathisb, aLaboratoire d'Application de la Chimie ~t l'Environnement, LACE/CNRS, Universitd Claude Bernard, Lyon L 43 Bd. du 11 Novembre 1918, 69622 Villeurbanne Cedex, France. bRdgie Nationale des Usines RENA ULT" Direction des Etudes Matdriaux, 8-10 avenue Emile Zola, 92109 Boulogne-Billancourt Cedex, France. Centre de Lardy, 1 Allde Cornuel, 92510 Lardy, France. Direction de la Recherche, 9-11 Avenue du 18 Jum 1940, 92500 Rueil Malmaison, France.

ABSTRACT In a general study of the role played by each component of three-way catalysts, a selective measurement of alumina and ceria surfaces area has been developed on model ceriaalumina supports. Three CeO2/Al20 3 solids (6.5, 13.4, 21 wt.% CeO2) were prepared by grafting Ce acetylacetonate on the surface of an alumina and calcination at 673 K. They were characterized by BET and X-ray diffraction measurements. The hydrogen temperatureprogrammed reduction (TPR) resulted in profiles similar to those of unsupported cerias, thus allowing an estimation of the equivalent surface area of ceria alone from the hydrogen uptake at low temperature. By adsorbing CO 2 on the OH groups of the alumina surface, hydrogenocarbonates species were formed and the IR band at 1235 cm -1 was selected to determine quantitatively the unpertubed alumina surface. In that case, by comparison with the BET surface area, it was possible to deduce an other value of the ceria surface area. The two sets of values obtained by these independent methods were found in good agreement, thus giving a good support for the reliability of each method. They show that the unpertubed alumina surface decreases when increasing the cerium content. Only 20% of the original alumina surface is preserved in the support containing 21 wt.% CeO 2.

406 1. INTRODUCTION Ceria and alumina, which form the intermediate porous layer (the washcoat) between the mechanical support and the supported metals and promotors, are important components in three-way catalysts (TWC) used for car exhaust gas cleaning. Although basic studies have been published on such systems [1], the interactions which can exist between alumina and ceria and which in turn may affect the interactions between the supported metal and the washcoat [2], are not fully understood. In particular, the multiple roles attributed to ceria, like stabilization of the alumina [3], of the supported metals [4], like storage and release of oxygen [2], are very probably dependent on preparation methods, activation and reaction conditions. Therefore, selective characterization of each oxide in ceria-alumina can be useful for a better understanding of the role played by both alumina and ceria in TWC. The present work describes two "chemical methods", the adsorption of carbon dioxide followed by IR spectroscopy and the temperature-programmed reduction (TPR), which lead to an estimation of the surface extent of alumina and ceria respectively.

2. EXPERIMENTAL

2.1. Preparation Cerium (III) acetylacetonate in toluene solution has been grafted on the hydroxyl groups of a powdered form of a transition alumina support (SCM129/Rhrne-Poulenc) in order to deposit ca. 3 Ce ions per nm2 of alumina surface ; the population of OH groups in alumina has been estimated to be 10 OH/nm2[5]. After reaction, the solid was dried in v a c u o (373 K, 10 h) and calcined under flowing oxygen (0.5 K/min, 673 K, 4 h). It is refered thereafter to as Ce3A1. Solids with 6 and 9 Ce ions per nm2 of alumina were prepared by repeating two times the previous procedure to give Ce6A1 and Ce9A1. After each grafting, the solids were dried and calcined as before. Unsupported ceria (HSA/Rhrne-Poulenc) and pure alumina (SCM129, Rhrne-Poulenc) were used as reference samples. These two oxides have specific surface areas of 127 and 107 m2/g, respectively. 2.2. Characterization Ceria-aluminas were studied by nitrogen adsorption at 77 K, in an automated volumetric set up built in the laboratory after a vacuum desorption at 773 K. All the BET measurements were refered to the initial mass of the sample.

407 The X-ray diffraction (XRD) pattems were obtained with a Siemens D5000 apparatus. Line broadening was used for the determination of the crystallite sizes. FTIR spectroscopy (BRUKER IFS 110) study of the adsorption of carbon dioxide on the solids was used to determine the free almnina surface area. More precisely, the adsorption of CO2 onto hydroxyl groups of the alumina produced characteristic bands of hydrogenocarbonate species [6,7]. The optical density of the band at 1235 cm -1, (~5 C-O-H bending mode), after taking into account the bands displayed by ceria, was measured and used to determine the free alumina surface. From this method and by comparison with total BET surface area, a ceria surface has been estimated. Ceria-aluminas, alumina and ceria were used as self supported wafers (0.01 to 0.03 g/cm2); they were thermally treated up to 673 K, under oxygen and then trader high vacuum, in situ, before adsorption of CO2 at room temperature. Then, the catalysts were evacuated at 295, 373, 473 and 573 K, for 1 h. IR spectra were recorded at room temperature, after CO2 adsorption and after each desorption temperature. The TPR experiments were performed in a set up described previously [8]. A weight amount of ca.0.2 g was located on the porous disc of a quartz microreactor, pretreated under a flow of air up to 673 K, for 1 h, then outgassed under argon flow (773 K, 1.5 h) and cooled to room temperature before a mixture argon + 1 vol.% hydrogen was deviated onto the catalyst. The heating rate (20 K/min), the flow rate (20 ml/min) and the final reduction temperature (1073 K) were kept constant.

3. RESULTS 3.1. Preliminary observations Table 1 gives the code of the samples, the ceria contents and the BET values. When increasing the cerium content, in the mixed solids, the BET surface area of the samples decreases but is always higher than that expected from the simple alumina contribution. For ceria-aluminas calcined at 673 K, X R detected small particles of ceria. A mean crystallite size obtained from the (100) and (200) lines broadening gave values of 4.2, 5.5 and 6.0 nm, for the three samples Ce3A1, Ce6AI and Ce9A1, respectively. Therefore, the preparation method using cerium (III) acetylacetonate does not lead to big supported ceria particles. However, it is known [1] that multiple cerium species exist in ceria-alumina and XRD alone may be insufficient to fully describe the cerium dispersion. Considering the literature data showing linear correlation between the low temperature hydrogen consumption during TPR and the initial surface area of unsupported cerias [9-11],

408 the TPR technique was applied to characterize the present ceria-aluminas samples. 3.2. Indirect determination of ceria surface area

A preliminary TPR-SM experiment was performed on Ce3A1 without in situ pretreatment before reduction. In addition to the expected hydrogen consumption at temperatures above ca. 623 K, the MS analyses show that the catalyst releases carbon dioxide, in three different steps, two of them peaking before 673 K. Therefore, the catalysts have been flushed in situ at 673K-773 K to eliminate the majority of COx species, before cooling to room temperature and initiating the TPR run.

1 Ce3AI 2 Ce6AI 3 Ce9AI r r := C

3

o} ot,..._

m

"O :=,,,

:E

,.,

200

4(~)0

560

6(X) 7130 860 Temperature K

9~

10~

1100

Figure 1 9TPR profiles corresponding to the ceria-alumina samples pretreated in air (673 K f o r 1 h) then under Ar (773 K f o r 1.5 h). H2/Ar = 1/99, heating rate 920 K rain -1.

The TPR profiles for Ce3A1, Ce6AI and Ce9A1, after in situ pretreatments, are shown in Figure 1. In previous experiments [9,11 ], TPR of unsupported ceria

409 have shown the presence of at least two important hydrogen uptakes, in agreement with literature data [1,2,10], one at moderate temperature (600-870 K) attributed to the reaction of hydrogen with capping oxygen ions, and a second one at much higher temperature due to the bulk reduction of ceria. The TPR profiles for supported ceria present two to three poorly resolved peaks, in the so-called low temperature domain (600-950 K), and a slowly decreasing consumption of hydrogen after stabilization of the temperature at 1073 K. The low temperature H 2 consumption phenomenon increases as the cerium content in the samples increases, but shows also that more than one chemical species is concerned. Since, the temperature for the beginning of this first phenomenon is rather constant, at ca. 600 K, the low temperature reduction peaks must always deal with the same type of cerium species.

Table 1: Alumina, ceria and ceria-alummas : summary of the results obtained in the present study. Code

CeO2 wt%

SBET m2/g

OD1235 /g

m1203

0 6.5 13.4 21.0 99.5

107 102 101 92 127

2.4 1.2 0.8 0.3 0

Ce3AI Ce6AI Ce9AI CeO2

SA1 SCel SCe2 m2/g cat. m2/gcat. m2/g 107" 54 36 13 0*

0 35 55 74 127

0 48 65 79 127

* values used for a linear relationship between ceria and alumina (FTIR spectroscopy) With the hypothesis that the hydrogen uptake at the lower temperature is characteristic of the reduction of Ce 4§ at the surface of cerium species, and taking into account the linear relationship between the initial surface area of unsupported cerias and the hydrogen consumption during the low temperature uptake [11], it is possible to convert each hydrogen uptake at low temperatm'e to an "equivalent initial surface area" of ceria (SCe 1). Table 1 reports the values of SCel deduced from TPR experiments, for the alumina-supported ceria and the reference samples. By increasing the cerium content, the value of SCel increases significantly; for Ce9A1, the value of SCel is almost 60% that of the reference ceria, whereas its ceria content is only one fifth of the total solid. Thus, the dispersion of ceria is rather high, as well as the coverage of the original alumina support by cerium species.

410 3.3. Indirect determination of the specific surface area of alumina

In order to cross-check the preceding results with a second "chemical" method, experiments able to detect selectively the fraction of alumina surface uncovered by ceria were looked for. As other alumina-supported oxides [12-16], adsorption of carbon dioxide was considered. Preliminary volumetric results of the adsorption of carbon dioxide at room temperature, after calcination and outgassing under vacuum at 673 K, were not fully conclusive, as both ceria and alumina are able to chemisorb carbon dioxide; further, although the adsorption strength of carbon dioxide is much lower on alumina than on ceria, experiments for isolating selective contribution of ceria, after desorption of CO2 from alumina at 373 K were also unsatisfactory, as some 20% of CO2 adsorbed on ceria was also desorbed during evacuation. Consequently, the IR spectroscopy of adsorbed C O 2 has been considered. IR spectra in the hydroxyl group range (3800-3400 cm-1), for both pure alumina and ceria, are shown in Figures 2a and 2b, respectively. Curves 1 refer to samples calcined at 673 K and outgassed at the same temperature and then, cooled to room temperature. Curves 2 refer to the catalysts after adsorption of CO2 at room temperature (pCO2 - 9-15 torrs) and curves 3 to the samples after a further evacuation at room temperature for 1 h. Curves 2 and 3 (Figure 2a) show by comparison with Curve 1 that the adsorption of CO2 on alumina generates a band at 3610 cm-1, stable after evacuation at room temperature. This band is attributed to the stretching mode of OH group in hydrogenocarbonate species [6,7], its intensity decreases after desorption at 373 K, for lh, and the band is completely eliminated after desorption at 473 K, for 1 h. As seen in Figure 2b (Curves 2 and 3), the adsorption of C O 2 o n CeO2 produces extremely complex spectra, both in presence of CO2 and after evacuation of the gas phase. Furthermore, the band at 3618 cm -1 is very close to the position of the hydrogenocarbonate species in the case of alumina. These two reasons are sufficient to eliminate the possibility to obtain selective measurement of surface properties of alumina in this region of the IR spectrum.

411

~)

3730

II

3670

g8 el 4D e~ el t... O

L._ 0

A~ el

36J0

\

|174 39OO

370O em-I

35OO cm-I

Figure 2 : FTIR spectra m the hydroxyl groups range for pure alumina (figure 2a) and pure ceria (figure 2b) : 1 : spectra after oxygen treatment at 673 K and evacuation at 673 K(alumina) 2 : introduction of C02 (10 torts) at 298 K for lh, 3 : desorption o f C02 at 298 K for l h. Figures 3a and 3b present the IR spectra of CO 2 in the 1100-1900 cm -1 range, for alumina and ceria respectively. Curves 1 refer to the samples in the presence of a pressure of 10 torrs of CO2 whereas curves 2 refer to the same solids aiter desorption at room temperature. In Figure 3a, a lot of absorptions are present; the vibrations at ca. 1860, 1820, 1775, 1705, 1437, 1320, and 1200 cm -1 show intensity stable or decreasing when the time of contact between CO2 and the catalyst increases; these bands are also greatly decreased after evacuation at room temperature. The more intense vibrations at 1648, 1483 and 1235 cm -1 have an intensity growing with the contact time and are still clearly visible after evacuation at room temperature. All the preceding bands decrease sharply ailer desorption at 373 K, the stability of the bands at 1648, 1483 and 1235 cm -1 being however higher than that of the others. After evacuation at 473 K, the surface of the alumina is freed from all these adsorbed species. These three main bands are

412 due to vibrations of hydrogenocarbonate species, whereas the others can be attributed, in agreement with literature data, to different forms of carbonates species [6,17,18]. _

1290

e8 gl

u

al

el

Q

u gl

e8 t.... o QpJ

tO

e8

_tn

el

1355 1

b 12.35

l

1900

I

1700

1

1

1500 cm-I

I

I

1300

1800

1600

1400

1200

em-I

Figure 3 : FTIR spectra in the carbonate groups range for pure alumina (figure 3a) and pure ceria (figure 3b). Pretreatment identical to Figure 2 : 1 : introduction of C02 (10 torts) at 298 K for lh, 2 : desorption of CO 2 at 298 K for lh.

The general aspect of the specmun of CO 2 species adsorbed on CeO 2 is practically not modified by evacuation at room temperature (Figure 3b), excepted the small shifts ofthe bands at 1730, 1354 and 1140 cm -1. All the bands at 1730, 1570, 1505, 1470 (shoulder), 1400, 1355, 1290, 1218, 1140, 1050 and 1040 (shoulder) cm -1 are attributed to carbonates and carboxylates species [19-23]. It is important to mention that the bands present at 1648 and 1235 cm -1 in the spectrum of CO2 irreversibly adsorbed on alumina, appear at positions allowing their discrimination fi'om the contribution of ceria. Therefore, they can be tentatively used to characterize free alumina surface in ceria-alumina samples.

413 Figure 4 shows the spectra of CO 2 irreversibly adsorbed at room temperature on the three ceria-altunina solids. All samples present a very wide absorbance in the region 1300-1700 cm-1, in which dominate the features of alumina (Ce3A1 and Ce6A1) or of ceria (Ce9AI). From Figure 4, it appears that only the band at 1235 cm -1 can be used with enough precision for the measurement of optical density. For all the other bands of the spectra, uncertainties in the position of the base line and strong shadowing of individual bands impede serious selective measurement.

1235

u ga

[ CeJAi ]

t._ O m

1800

1600

144}@

1200

9

Figure 4 9FTIR spectra of CO 2 adsorption onto ceria-aluminas samples. The solids were calcined under oxygen at 673 K and evacuated at the same temperature. C02 (10 torrs) was introduced at 298 K f o r 1 h and evacuated f o r 1 h at 298 K.

The values of the optical density of the band at 1235 cm -1 expressed per gram of sample are also given in Table 1, and are converted in terms of not modified surface of alumina, SA1, using a linear relationship between the optical density of the 1235 cm-1 band for pure alumina and a value 0 for pure ceria. The difference

414 between the total surface area of ceria-alumina (BET method) and SA1 measured from the preceding data is noted SCe2; the values of SCe2 are also reported in Table 1. For the ceria-aluminas solids of the present study, the two sets of values SCel and SCe2, obtained by completely independent methods, are in relatively good agreement.

4. DISCUSSION

Ceria-aluminas have been studied in the past by different techniques, like TPR, Raman spectroscopy, XRD and XPS [1,2,10,24,25]. For ceria-alumina prepared by impregnation with cerium (III) nitrate and calcined for 16 h at 7731073 K, TPR up to 1173 K showed poorly resolved TPR traces. The TPR profiles display one main TPR peak at low cerium loading and at least 3 hydrogen uptakes for cerium loading arotmd 21 wt.% [2]. Apparently, all Ce 4+ ions were reduced to Ce 3+ at the end of the TPR [2]. For other ceria-aluminas containing 1 to 17 wt.% ceria, prepared by impregnation of a non microporous alumina (alumina C/Degussa, 1002/g) with aqueous solution of cerium (III) nitrate, drying and calcination at 1073 K for 4 h, the presence of three different types of cerium species was advocated [1] : a species in close interaction with the alumina and refered to as "precursor of cerium aluminate", small particles of ceria with size lower than the XRD detection limit and ceria particles with size equal to or higher than 20 nm [1]. The former species would be prevalent at low ceria loadings, whereas the latter ones would exist mainly for highly loaded samples. In this second study, TPR results suggested that the precursor of the cerium aluminate is "partially" reduced at around 673 K and fully transformed to the aluminate at ca. 1000 K, whereas the small ceria particles and the large ceria particles would be reduced around 873 K and above 1073 K respectively. Later, with unsupported cerias of different specific surface areas, a reduction model was proposed, consisting in reducing first "capping" oxygen ions, during the low temperature peak, before reducing bulk ceria at higher temperatures [2,10]. Such a reduction model has been extended to other samples of unsupported cerias with larger surface areas, using both TPR and a selective quantification of Ce 3+ through magnetic susceptibility measurements [9,11 ]. More precisely, a linear relationship between the initial specific surface area of ceria and the hydrogen consumed during the low temperature TPR peak, has been observed. A consumption 4.2 lamol H2/m 2 of CeO2, during the TPR, has been estimated [ 11 ].

415 The preceding results suggested that during the reduction of ceria, bulk reduction is very much slower than surface reduction, leading to a possible "selective measurement" of reducible species at the ceria surface. In the present study, with the hypothesis that the density of the reducible oxygen ions at the surface of supported cerium species is similar to the one found in unsupported ceria samples, it was possible to transform the hydrogen uptake of the low temperature TPR phenomenon, during the reduction of ceria-alumina, in "initial equivalent ceria surface", SCel. The values reported in Table 1 increase with the cerium loading, and seem consistent with a rather high coverage of alumina by cerium containing species, as expected from the grafting method used for the preparation. The high coverage of alumina by cerium species in the present samples is sustained by the comparison of the Ce/A1 atomic ratios measured by XPS, in the present catalysts and in the ones described by Shyu et al. [1 ]. In our case, the atomic Ce/A1 ratio was found close to 0.3, for the ceriaalumina with 21 wt.-% ceria, whereas Shyu et al. [1] measured only 0.03 in a catalyst containing some 20 wt.% ceria. However, the specific surface area of ceria in ceria-alumina, as measured by TPR, is quite different from the values deduced from X-ray line broadening. This difference can be explained as the area calculated from XRD is 50% lower than the area calculated from TPR : XRD detects only ceria crystallites with a "sufficient" crystallite size, whereas TPR measures all reducible surface species, even those considered as CeA103 precursor. In addition, with very small ceria particles or with phases prepared at rather low temperatures, numerous surface defects are probably able to interact with subsurface cerium species [11,26], and lead to hydrogen uptake higher than expected from a strict surface phenomenon. Anyway, considering that the low temperature TPR peak includes multiple cerium species, the difference between the cerium surface obtained by TPR and that deduced from XRD would represent the surface of cerium species in strong interaction with the alumina, a measure which could give deeper insight into the structure of ceria-aluminas. The uncertainties discussed in the preceding section prompted us to look for another "chemical method" to estimate the surface of supported ceria. As for alumina-supported oxides [12-16], the adsorption of CO2 has been considered, IR spectroscopy being prefered, with the aim of finding vibrations specific of CO2 interacting either with ceria or with alumina. This method has been applied although very recent results, mainly with alumina supported molybdenum questionned the validity of CO2 adsorption to measure the coverage of alumina

416 by supported oxides [15,16]. In fact, these studies indicate that only a very limited fraction of the alumina OH groups are able to interact with CO2 and that these OH are also those linked to the supported molybdenum species. However, if the use of total adsorption of CO2 to estimate alumina coverage by supported oxides can be questionnable [15,16], the use of IR bands characteristic of HCO3" must give a reasonnable answer. The results presented in Figures 2 to 4, confirmed the very complex situation of adsorbed CO2 species at the surface of both alumina and ceria. However, the present results are in agreement with literature data [17-19,21]. With the hypothesis that neither the nature of the OH groups nor the formation of hydrogenocarbonate species on the alumina are modified by the presence of supported ceria (hypotheses well verified for Ce3A1 and Ce6A1, in the OH region of IR spectra), it has been possible to calculate a free alumina surface in the mixed solids using the optical density (OD) of the band at 1235 cm -1, since this band does not appear with pure ceria, and its frequency is not affected by the ceria presence. Although a more intense hydrogenocarbonate band, at 1645 cm -1 (symmetric C-O-H stretching), can also be used for this purpose, the problematic measure of its optical density made its use non reliable. The results from CO2 adsorption have been compared with those deduced from TPR. Considering the rather good agreement between the values reported in Table 1, each method seems to support the other. Therefore, two different chemical methods allow to calculate selectively the surface area of alumina-supported cerium species. It is important however to recall that for a true quantitative determination of the hydrogenocarbonate species by IR spectroscopy, the exact nature of the alumina and the thermal treatments which easily modify the hydroxyl population (type and number) have to be very well controlled. In the case of using TPR for estimating the coverage of alumina by ceria, it is necessary that all cerium species are initially in the Ce4+ oxidation state. Such a situation is probably not always warranted in samples calcined at a temperature high enough to form Ce 3+, in cerium aluminate phase. Further work is in progress to answer these questions.and to apply this methodology to industrial catalysts.

417 5. CONCLUSION

The aim of this work was to find a general method to discriminate ceria and alumina surface in ceria-alumina supports. Two methods were applied based either on the selective reduction of the ceria surface or the use of the 1235 cm, 1 IR absorption band specific of the adsorption of CO2 on the surface hydroxyl groups of alumina. The rather good agreement between the results obtained by the two methods supports the validity of the hypotheses made in each case. The main limitation concerns the possible modifications which may occur in the hydroxyl groups population of the alumina after various thermal and chemical treatments. ACKNOWLEDGEMENT

The technical assistance of Mr. J. Billy for infrared experiments is gratefully acknowledged.

REFERENCES

10 11

J.Z. Shyu, W.H. Weber and H.S. Gandhi, J. Phys. Chem., 92 (1988) 4964. H.C. Yao and Y.F. Yu Yao, J. Catal., 86 (1984) 254. B. Harrison, A.F. Diwell and C. Hallett, Platinum Met. Rev., 32 (1988) 73. J.C. Summers and S. Ausen, J. Catal., 58 (1979) 131. A.V. Kiselev and V.I. Lygin (eds.), Infrared Spectra of Surface Compounds, J. Wiley and Sons, New York, (1975), p. 237. J.B. Peri, J. Phys. Chem., 70 (1966) 3168. C. Morterra, A. Zecchina, S. Coluccia and S. Chirino, J. Chem. Soc. Faraday Trans. I, 73 (1977) 1544. F.M. Zotin, L. Tournayan, J. Varloud, V. Perrichon and R. Frrty, Appl. Catal., A General, 98 (1993) 99. A. Laachir, V. Perrichon, A. Badri, J. Lamotte, E. Catherine, J.C. Lavalley, J. E1 Fallah, L. Hilaire, F. Le Normand, E. Qurmrrr, G.N. Sauvion and O. Touret, J. Chem. Soc., Faraday Trans. I, 87 (1991) 1601. M.F.L. Johnson and J. Mooi, J. fatal., 103 (1987) 103, and 140 (1993) 612. V. Perrichon, A. Laachir, O. Touret, G. Bergeret, R. Frrty and L. Tournayan, J. Chem. Soc., Faraday Trans. I, 99 (1994) trader press.

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Catalysis attd Automotive Pollution ControlIII


419

INFLUENCE OF THE NATURE OF THE METAL PRECURSOR SALT ON THE REDOX BEHAVIOUR OF CERIA IN Rh/CeO2 CATALYSTS S. Bemala, J.J. Calvinoa, G.A. Cifredoa, J.M. Gaticaa, J.A. P6rez Omila, A. Laachirb and V. Perrichonb aDepartamento de Ciencia de Materiales, Ingenieria Metal~rgica y Quimica Inorgdnica. Facultad de Ciencias. Universidad de Cddiz. Apartado 40. Puerto Real. 11510 Cddiz. Spain. bLACE/CNRS, Universit~ Lyon I, IRC. 2, Avenue Albert Einstein. 69626 Villeurbanne Cedex. France.

ABSTRACT The hydrogen chemisorption on two Rh/CeO 2 catalysts prepared respectively from rhodium nitrate and rhodium chloride has been studied. The evolution of the ceria oxidation state with the series of treatments applied was monitored by means of a magnetic balance. Temperature Programmed Reduction and Oxidation (TPR/TPO) as well as Volumetric Adsorption techniques have also been used. Upon treating with H2, at 623 K, the Precursor/Support systems, the reduction level reached by ceria was 11.4% for the sample prepared from Rh(NO3)3 and much higher, 22.1%, for the chlorine containing catalyst. In the later case, the reduction degree varied very slightly with succesive evacuation/hydrogen adsorption cycles. This contrasts with the behaviour observed for the sample prepared from rhodium nitrate, for which the reduction process is to a much larger extent reversible. The results reported here for RhCI3/CeO 2 are interpreted as due to the substitution of the ceria lattice oxygen ions by el-, thus blocking the operation of both the direct and incorporation of el- into the support. This induces a much higher irreversible reduction of ceria as well as the blocking of both the direct and back spillover processes responsible for the reversibility of the ceria reduction by hydrogen.

420 1. INTRODUCTION It is generally acknowledged that the redox behaviour of ceria plays an important role in determining its singular properties as metal support and promoter [ 1,2]. We have recently shown that, in the presence of rhodium, ceria can chemisorb large amounts of hydrogen via a spillover process [3,4]. As deduced from magnetic measurements, this type of adsorption modifies the ceria oxidation state inducing a very strong increase of the concentration of paramagnetic Ce 3+ ions [3-5]. Upon further evacuation, ceria becomes to a large extent reoxidized, thus indicating that there is an important reversible contribution to the final reduction degree reached by ceria [3-5]. The observations above were made on Rh/CeO2 samples prepared from Rh(NO3)3, however, we noted in ref. [6] that the behaviour of catalysts prepared from RhC13 was significantly different. This prompted us to carry out the present study, the major objective of which was to investigate the influence of chlorine on the chemisorptive and redox properties of ceria. For this purpose, two Rh/CeO 2 catalysts prepared by impregnating the same ceria sample with either Rh(NO3) 3 or RhC13 were investigated by means of a Faraday magnetic balance, Temperature Programmed Reduction/Oxidation (TPR/O) and Volumetric Adsorption techniques. Since chlorine containing noble metal precursors are often used in the preparation of TWC's and related catalytic systems, the present work would provide some clues helping us to understand the behaviour of this very important family of catalysts.

2. EXPERIMENTAL

The ceria sample used here was a medium-surface area sample (49 m2.g-1) prepared in the laboratory by calcining at 873 K, for 4 h, a cerium hydroxycarbonate precipitate obtained by addition of ammonium carbonate to a solution of Ce(NO3)3. To eliminate the residual carbonate, it was further treated with flowing H 2 at 773 K for 4h, and finally reoxidized in air at 773 K for 4 h. The surface area of the ceria sample did not significantly change throughout the whole series of treatments applied in the present work. The Rh/CeO2 catalysts were prepared by incipient wetness impregnation technique using an aqueous solution of either RhC13 or Rh(NO3) 3. The precursor/support systems were dried in air at 383 K for 10 h, and stored in a dessicator with no further precautions. The metal loading of the two samples above, hereafter referred to as Rh(C1)/CeO2 and Rh(N)/CeO2 respectively, was 3% by weight.

421 The Faraday microbalance used here has been described elsewhere [7]. Details about the procedure we have followed to determine the magnetic susceptibility of the Rh/CeO2 catalysts are reported in refs. [3,8]. The experimental values, which were corrected from the traces of ferromagnetic impurities (6-12 ppm), allowed us to determine the content of paramagnetic Ce 3+ ions, and therefore the percentage of Ce 4+ ions reduced to the 3+ oxidation state [8]. The magnetic contribution of rhodium was considered to be negligeable (Maximum value to be expected: 3.10 -8 emu CGS at 298 K, to be multiplied by 12.56 to obtain SI units in m3.g-1). The experimental device used in Temperature Programmed Reduction/Oxidation (TPR/TPO) studies was similar to that described in ref. [9]. The quadrupole mass spectrometer used to analyse the evolved gases was a VG Spectralab SX-200 instrument interfaced to a PC-type microcomputer. The experiments were run under the following conditions: Flow rate of H2 (02): 60 cm3.min - 1; Heating rate: 10 K.min- 1. Hydrogen volumetric adsorption measurements were carried out in a conventional high vacuum system equipped with a capacitance gauge, MKS Baratron, model 220 BHS. The time spent between succesive isotherm points was routinely 20 minutes. The final hydrogen pressure was 300 Torr.

3. RESULTS 3.1 Magnetic Susceptibility Study Table 1 summarizes the results obtained from the magnetic susceptibility study carried out on both Rh(C1)/CeO2 and Rh(N)/CeO2 catalysts. This study was aimed at investigating the evolution of the ceria redox state upon submitting the catalysts to a number of treatments including the initial reduction step at 623 K, several hydrogen adsorption/evacuation cycles, a series of reoxidation experiments at increasing temperatures from 295 K to 773 K, and finally a new hydrogen reduction at 623 K of the reoxidized sample. As deduced from Table 1, before the first hydrogen treatment, the RhC13/CeO 2 sample was slightly paramagnetic, thus indicating the presence in it of some Ce 3+ ions (Percentage of Ceria Reduction: 0.4%). After the reduction treatment at 623 K, for lh, in a flow of H2 (60 cm3.min-1), at a heating rate of 10 K.min -1, followed by cooling to 295 K, also in flowing H2, the percentage of Ce 3+ present in the catalyst was found to be equal to 22.1%. This value remained constant upon evacuation at 295 K; moreover, it diminished very slightly after pumping off the sample (P99.9% AI2(OH)6 with Na20 impurity of 0.06%, and was of mean particle diameter 39.0 mm. Pseudo-boelunite (Pural 200) was obtained from Condea. Aluminium sulphate from Ajax Chemicals (AR grade) had a purity of >97.0% with less than 0.05% sodium (Na) impurity, and less than 0.01% insoluble matter. Concentrated sulft~c acid (98%) was supplied by Ajax. Some samples were doped by adding small amounts of La(NO3)36H20 (Aldrich Chemicals: 99.99% pure) or Ba(NO3)2 (Ajax: 99.5% pure) 2.1 Sulphation Initial experiments attempted to react gibbsite with concentrated sulphuric acid. Conversions were low as a result of fonnation of a surface layer of aluminium sulphate which restricted fiarther sulphation. Subsequent experiments were carried out with a fixed ratio of 98% sulphuric acid: gibbsite (1.92:1 - calculated to be the ratio required to convert 100% of gibbsite) hi the presence of varying amounts of water. Conversion was found to be highest at an acid: water: gibbsite ratio of 1.92:2.02:1. Subsequent sulphation was carried out using a standard procedure. 100g gibbsite were mixed with 200 ml distilled water and stirred. 194.5g of 98% H/SO4 were added slowly and with stirring. The temperattu'e was controlled at about 110~

433

for 30 min, after which time the products were poured into a mould where total solidification occurred.

2.2 Doping Several methods of doping were tested, using 2 mol% La203 (calculated with respect to final alumina) or 4 mol % BaO, both added as nitrates. No significant differences were observed between adding dopant to the solution of aluminium sulphate before cooling or to solid aluminium sulphate after drying (see below). A general procedure was adopted in which a solution of the dopant nitrate was added to the sulphurisation beaker during the heating/stirring period and before cooling and dehydration. 2.3 Drying/calcination/grinding The sulphate samples were broken up and dried at 150-200~ (5h) and 600~ (either 2 or 4h, depending on the mass of material). Conversion of the sulphate to alumina was achieved by calcining in air at 1000~ for 4h. The reasons for the choice of these conditions are given below. Grinding was carried out in a ball mill, using 50g alumina mixed with 250ml water. Both pure and doped alumina were grotmd. 2.4 Characterisation of products Surface areas were measured using a Micromeritics 2200 high speed surface area analyser: reproducibility was _+ 2%. X-ray diffraction patterns were obtained using a Rigaku powder diffractometer with CuKa radiation. Particle sizmg was accomplished using a Malvem Mastersizer. Water absorptivity was measured by adding demineralised water to 5g of dried alumina until the mixture just became fluid. The amount of water required was measured and the percentage solids calculated. Reproducibility was +_ 1%. 3. RESULTS AND DISCUSSION

Important properties for a washcoat alumina include surface area/porosity/thermal stability, particle size and coatability. The preparation of alumina from gibbsite via the sulphate was checked with respect to these properties. The conversion of gibbsite to aluminitma sulphate was measured in terms of the weight gain, on the assumption that, after dehydration, the product of the reaction was A12(SO4)3. The initial reaction resulted in the formation of a solid product containing large amounts of water of crystallisation, but this water could be removed during drying.

434

ml2(OI--I)6 -~- 3HzSO, +

12HzO = A12(SO4)3 18H20

A H = -433 U/mole

The importance of water to the sulphation was shown by the fact that 120 m2g~ could be produced by calcination. The alumina derived from Ajax ahuninium sulphate had a surface area between 120 and 130 m2g~. X-ray diffraction showed that %,-alumina was the major product.

435 lt~O

II

r 120 E

-

L_

100 80

(1)

=

O

5A from any tin atoms, the result of calcination is to incorporate the copper ions into the tin oxide lattice. Calcination of the same sample at 600~ essentially removes all the initial [Cu(H20)6] 2+ sorbate, and only the lattice-bound copper species is present. The

494

01-12 H

~0

H

H

.0

H

H

H20" ..... [ ,,,,,,,' OH 2

_q

H20~"

I OI-t2 Cu.~,

l

.o.

H

H

H

9 H O

~.

H O

O %

H O

H O

I

I

I

I

:o

H

H

.oo.o

9

[Cu2+]aq

I

H

H

I

I

~,..9 >5A

Sn O Sn O Sn O

Sn O Sn O Sn O Sn

IIIIIIIIIIII IIIIIIIIIIIIIIIIIIIIIIII IIIIIIIIIIII IIIIIIIIHIIIIIIIIIIIIIIIIIII

IIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIII HIIIIIIHIIIIIIIIIIIIIIIIIIIIIIIIIIIIIII

room temperature

calcination at 300~

OH 2

H20%' ! '"'""OH2 H20~ ~'~' [ u ~ O H 2

.o.

H

0

0

0

0

I

I

I

I

calcination at 600~ -~

I:I

H

O

()

O

O

O

O

I

I

I

I

I

I

Sn O Sn O Sn O Sn O Sn O Sn .,.,,.,,,,,,.,.,a,,,,.,,,,.,,,,,,,,,,,,,,.,,,,..,.,,,,

Sn O Sn O Sn O Sn

IIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIII IIII IIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIII

IIIIII IIIIIIIIIII IIIIIIIIIIIIIIIIIIIIIIIIIIIIIII IIIIIIII IIIIIIIII

Sn O Sn O Sn O Sn O C u O S n IIIUlIIIIIUlIUlIIIIIIIIIIIIUlIIIIUlIIIIIIIIIIIIIIIIUlIUlII

Sn O Sn O C u O S n

III I IIIIIIII IIIIIIIIIIIIII II III IIIIIIII I I

Scheme 1

495

processes are illustrated schematically in Scheme 1. No evidence for any intermediate covalently bound surface copper species could be detected. In contrast, FT-ESEEM spectra of the second sample, that prepared by coprecipitation, exhibit both hydrogen mad tin-119 frequencies for the freshly prepared sample. The conclusion, therefore, is that preparation of SnO2-Cu2+ catalyst smnples by coprecipitation results in the incorporation of copper into the tin(IV) oxide lattice as well as sorption of [Cu(H20)6] 2+ cations on to the oxide particle surface.

4 CATALYTIC ACTIVITY

Catalytic activity studies were carried out using a typical catalytic microreactor. Catalyst sample sizes were 0.5g for CO oxidation studies and 2.0g for n-propane oxidation studies. Flow rates of the gas mixtures, which varied from stiochiolnetric to oxygen-rich, were in the range 90100 ml min -1. Table 3 SUlmnarises the activity of selected Sn-Cu-O, SnTable 3. Temperatures necessary for the complete removal of CO and n-propane over Cu-Cr-Sn-O catalysts together with specific activities

Catalyst

T100(CO) /oca

TI00(C3H8 /ocb

Spec. Act.

(co)c

Spec. Act. (C3H8) c

0

360

525

0.06

71Sn 29Cu-O

150

400

0.53

0.82x10-3

77Sn-23Cr-O

250

280

0.072

8.4x10-3

62Sn-19Cu-19Cr

175

310

0.43

5.9x10-3

200

400

0.064

1.6x10-3

SnO2

Pt/AI203

(a) (b) (c)

Temperature required for the complete removal of CO. Temperature required for the complete removal of C3H8. Moles converted/g catalyst/h at 300~ at complete conversion.

496 Cr(VI)-O and Sn-Cu-Cr(VI)-O catalysts for the oxidation of CO mid npropane compared with tin(IV) oxide itself and a comparable aluminasupported platinum catalyst. Activity towards oxidation of CO of the catalysts is good if copper is present with specific activities which are approximately ten times that of a comparable alumina-supported Pt catalyst. Light-off temperatures tend to be lower than 100 ~ with complete conversion occurring below c a . 150 ~. In contrast, catalysts containing chromium(VI) enhance the conversion of propane, and the Sn-Cu-O catalysts performed less well than either the Sn-Cr(VI)-O or Sn-CuCr(VI)-O catalysts. Again, specific activities compare favourably with the alumina-supported Pt catalyst. The best performance is exhibited by the mixed Sn-Cu-Cr(VI)-O catalysts which are efficient for the removal of both CO and propane. Figures 5 and 6 illustrate the comparative performances of the tin(IV) oxide catalysts together with data for commercial copper chromite for both the conversion of CO and propane. REFERENCES

EC Directive Dir. 88/76/EEC, December 1987. See also Directives Dir. 88/436/EEC, 16 June 1988, and Dir. 89/458/EEC, 18 July 1989. EC Communication COM (89) 662, 2nd February 1990. G. Michel and R. Machiroux, J. Ramma Spectrosc., 1983, 14, 22; 1986, 17, 79. F. Gonzalez-Vilchez and W.P. Griffith, J. Chem. Soc., Dalton Trans., 1972, 1417. M.A. Vuunnan, Doctoral Dissertation, University of Amsterdam, 1992.

ACKNOWLEDGEMENTS: We thank the Science and Engineering Research Council and the Govenunent of Malaysia for support. Dr. Daniella Goldfarb mid Mr Khalid Matar for the EPR and ESEEM measurements, and Dr. Carole C. Harrison for assistance with the electron microscopy.

Diesel Catalyst Technologies



CATALYTIC

OXIDATION OF DIESEL PARTICULATES BASE METAL OXIDES

499

WITH

K.E. Voss, J.K. Lampert, R.J. Farrauto, G.W. Rice, A. P u n k e and R. K r o h n

Engelhard Corporation, 101 WoodAve., Iselm, NJ 08830-0770, USA and Engelhard Technologies GmBH, Misburger Strasse 81b, Hannover, Germany

ABSTRACT

Reduction of emissions from diesel engines using novel flow-through oxidation catalysts containing base metal oxides has been demonstrated. The soluble organic fraction (SOF) of the particulates can be converted and gas phase hydrocarbons can be removed via the proper choice of oxides. Low levels of platinum on the catalysts also compliment HC and CO conversion without leading to "sulfate-make". Catalyst performance is shown for transient and steady state engine testing relative to emissions standards for U.S. truck and European auto applications. Laboratory studies using PYRANTM thermal chromatographyand engine storage & release test results provide insight of the mechanisms of removal and conversionof SOF and HC's by the catalysts.

1. INTRODUCTION The exhaust emissions from a diesel engine are composed of three phases: solids, liquids and gases. The combination of solids and liquids comprise the so called particulates, or total particulate matter (TPM), of the emissions. These particulates in turn are composed of: dry carbon (soot), liquid hydrocarbons and "sulfate". The dry carbon comes from the incomplete combustion of the fuel and because it is principly a solid, a flow-through type catalyst typically has little effect on this fraction of the particulates. The main liquids present in the particulates are a combination of lighter unburned fuel and lubricating oil, e.g. swept from the cylinder walls. Together these are the so called soluble organic fraction (SOF) or volatile organic fraction (VOF) which are in the form of discrete aerosols and/or are adsorbed on the dry carbon

500 particles [1]. It is this liquid fraction of the particulates which a flow-through catalyst can remove and oxidize. When diesel fuel is burned in the engine most of the sulfur it contains is oxidized to SO2 which is emitted in the gas phase. However, a portion of the sulphur is oxidized completely to SO3 which in turn combines with the moisture in the exhaust and becomes condensed H2SO4 or "sulfate" which adds to the particulate emissions. Because of this an effective diesel catalyst must minimize any additional oxidation of SO2 to SO3. The gas phase emissions of interest are composed primarily of hydrocarbons, carbon monoxide, nitrogen oxides and sulfur. Diesel emissions are clearly more complex than those from a spark ignited gasoline engine, and thus their reduction by catalytic treatment is much more complicated, requiting new technology. Control of diesel emissions is being addressed worldwide. In the U.S., Europe and Japan most of the trucks and buses operate with diesel fueled engines. Each vehicle or engine must meet specific standards as measured by standardized emissions tests which reflect the duty cycle anticipated for the particular engine. Within the U.S. a significant reduction in allowable TPM emissions for medium and heavy duty trucks has been required for MY 1994 with a standard of 0.10 g/hp-hr, down from 0.25 g/hp-hr prior to 1994 (see TABLE 1).

Table 1U.S. Heavy~Medium Duty Diesel Emissions Standards (HD U.S. Transient Test Cycle) Mass Emissions (g/HP-hr) Year HC CO NOx TPM 1991

1.3

15.5

5.0

0.25

1994

1.3

15.5

5.0

0.10

This reduction for the most part can not be achieved via engine modifications alone making exhaust attertreatment required. Generally, in the U.S. medium and heavy duty engines meet the standards for gas phase hydrocarbon, carbon monoxide and nitrogen oxides for MY 1994. The emissions test is conducted using the heavy duty U.S. transient (FTP) cycle which reflects a continuous measure of emissions during various speed and loads reflecting urban and expressway driving [2]. The transient test itself and different engines with different power ratings, result in a variety of exhaust temperature and flow conditions. Thus, the catalyst must remove and convert the particulates over a broad range of conditions.

501 A newly developed catalyst, containing a proprietary, non-toxic base metal oxide as the active material for eombusting the SOF portion of the particulates, is now commercialized in the U.S. to meet these standards [3]. In Europe, diesel passenger ears must meet standards reflecting both urban and high speed driving conditions. The standards are given in TABLE 2 below.

Table 2European Diesel Passenger Car Emissions Standards (European Transient Test Cycle) Mass Emissions (g/km) Timing HC + NOx CO EURO I Current 0.97 2.72 EURO II 1996 IDI 0.70 1.00 DI 0.90 EURO III

1999

0.50

0.50

TPM 0.14 IOl 0.08 DI 0.10 0.04

The current standards are scheduled to become stricter in 1996 (EURO II) and as proposed again in 1999 (EURO III). In addition to particulates, the catalyst is also required to reduce gas phase HC and CO emissions. The European Transient Test (Cycle A) evaluates emissions on the basis of low speed urban (ECE) and high speed (EUDC) driving segments [2]. For the overall test cycle the weighting for the ECE segment (avg. 19 km/hr) is approximately twice that of the EUDC segment (avg. 63 km/hr). Although catalyst inlet temperatures for the EUDC segment of the test can run between 200 ~ and 550~ they are typically quite low for the ECE segment (100-250~ As a result an effective catalyst must operate over a broad range of temperatures and low temperature removal of emissions and catalyst light-off are significant challenges. Especially challenging is the requirement for CO and HC conversion durng the low temperature ECE segment. Increasing the precious metal content will reduce the temperature for gas phase oxidation. However, this adds significantly to the cost of the catalyst since precious metals are expensive and furthermore, can be highly active towards the oxidation of SO2 to SO3 during the higher temperature EUDC portion. Consequently, alternative materials, which use a minimum of precious metals, would be more desirable. The work reported in this paper describes the results of engine and vehicle tests of diesel oxidation catalysts containing base metal oxides for the combustion of the SOF portion of the particulate emissions and of a new generation of diesel oxidation catalysts specifically formulated for European passenger car applications. This new family of catalysts is based on the technology developed for the U.S. truck catalyst but also contains other proprietary non-toxic, inexpensive base metal oxide components which enhance the reduction of

502 hydrocarbons at low temperatures without producing excessive amounts of sulphate. This is accomplished with relatively small amounts (< 30 g/it 3) of precious metals. A laboratory method simulating the adsorption and subsequent catalytic combustion of the soluble organic fraction (SOF) on these newly developed diesel oxidation catalysts, is also described in this paper. This technique, based on thermal chromatography, allows characterization of the initiation of catalytic oxidation and analysis of the products giving insight into the mechanism of operation. 2.

MEDIUM DUTY DIESEL ENGINE TEST RESULTS

We have reported previously [3, 4] on the performance of diesel oxidation catalysts containing base metal oxides for SOF combustion and low levels of platinum for gas phase HC and CO reduction without production of "sulfate". This type of catalyst, designated in this paper as Catalyst "C", for the U.S. diesel truck application has given emissions reduction performance in the Heavy Duty Transient Test (FTP) as shown in TABLE 3. For this test the platinum loading of Catalyst "C" was 0.5 g/fi3 or approximately two orders of magnitude lower than a conventional three way catalyst for SI gasoline applications. The tests were nan using a MY 1991 5.9 liter DI/TCI engine rated at 190 HP which produced a maximum exhaust temperatm'e of 305~ in the FTP test. The catalyst was coated onto a 9" dia.x6" long ceramic substrate (6.25 liters) having 400 cells/in2. Low sulfur fuel (0.05 wt% S) was used for catalyst evaluations. Preconditioning and aging of the catalysts were done on an engine using fuel with a sulfur content of 0.3 wt% S. Table 3Catalyst "C"- U.S. HD Transient (FTP) Emissions Test Results Mass Emissions (~/HP-hr) Emission Engine-Out Catalyst"C" Fresh 1000 hr Aged Component Engine-Out ~Fresh) * 1. Total Particulates 0.172 0.116 a. SOF 0.061 0.026 b. Sulfate 0.004 0.002 2. Gas Phase a. HC 0.299 0.188 b. CO 1.49 1.11 Fresh = Preconditioned on the engine for 24

% Removal

% Removal

33 58 55

33 53 23

37 26 hrs.

29

9

503 As can be seen Catalyst "C" gives a high level of SOF removal (58%) on this engine which contributes to a removal of 33% of the total particulates (TPM). Furthermore, the particulate removal performance is stable over extended periods of engine aging (1000 hrs). The MY 1991 engine meets the pre-1994 TPM and gas phase emissions standards without a catalyst. Catalyst "C" gives a substantial reduction in the SOF emissions. However, to meet the 1994 emissions targets further reductions in the "Dry Soot + Other" component of the particulates through new engine technology was also needed. This has been accomplished, and through joint catalyst development and engine development the TPM targets have been met for U.S. truck applications. Inspite of the extremely low platinum loading level of this catalyst and the low engine exhaust temperatures in the test, it gave relatively good conversion of gas phase HC and CO (37% and 26%, respectively) in the flesh state. Gas phase activity was decreased; however, after extended engine aging. U.S. emissions standards (LEV & ULEV) in the late 1990's will require catalysts with improved HC removal and probably at least some NOx reduction activity, as well. Emissions standards for diesel autos in Europe will require improved HC removal to meet EURO II levels for HC + NOx. Catalyst "C" has been reformulated with additional oxide components and varying precious metal loadings to address these needs. The new type of catalyst, designated Catalyst "D" in this paper, has been found to exhibit improved HC removal, especially at low exhaust temperatures. Steady state engine tests were conducted using a MY 1991 5.9 liter DI/TCI diesel engine rated at 230 HP nmning on low sulfur fuel (0.05 wt% S). The steady state test modes were chosen from the European R-49 Test Procedure which gave different catalyst inlet temperatures ranging from ca. 120 to 550~ Tests comparing Catalyst "C" and Catalyst "D" were run. Each catalyst was coated onto a 9" dia. x 6" long ceramic substrate with cell spacing of 400 cpsi. Gas Phase H C C o n v e r s i o n

(a)

(b)

~

Catalyst "D" eO

-

~

20 ~o

*

150

i

200

I

i .

300

Catalyst I n l e t

i

380

|

400

Temp.

Removal

atalyst "D"

i

60

9

Catalyst "C"

Clltalyst "C"

280

SOF

2o ~

480 (deg

i

500 C)

i

550

000

~o

i

160

i

200

i

280

i

300

Catalyst I n l e t

i

380

|

400

Temp.

i

i

460

800

(deg

C)

Figure 1. - Steady State Engine Performance of Catalysts "C" and "D"

i

S60 CO0

504

For these tests both Catalyst "C" mad Catalyst "D" had platinmn loading levels of ca. 2 g/ft3. The test results for gas phase hydrocarbon conversion and SOF removal and conversion are shown in Figure 1a and lb, respectively. As can be seen the reformulated Catalyst "D" exhibited substantially better removal of gas phase HC's at catalyst inlet temperatures in the 120-200~ range. At temperatures of ca. 300~ mad above both catalysts gave comparable HC conversion. Thus Catalyst "D" gave a high level of HC removal and conversion (>60%) over the entire exhaust temperature range and with a very low platinum loading level. This improved HC removal is the type needed to address the coming European diesel auto and future U.S. diesel truck and bus emissions requirements. Catalyst "D" also exhibited slightly better overall SOF conversion than did Catalyst "C". 3.

EUROPEAN DIESEL PASSENGER CAR TRANSIENT TEST RESULTS

The improved HC removal and conversion of Catalyst "D" was demonstrated filrther for the diesel auto application through European Transient Testing using a chassis dynamometer. The test vehicle had a 2.5 liter DI/TCI engine with EGR and was run on low sulfi~r filel (0.05 wt% S). In the tests the engine gave catalyst inlet temperatures in the range 100-200~ for the urban driving (ECE) segment and in the range 200-355~ for the high speed (EUDC) driving segment. Overall this represented a cool numing engine and thus a challenge for catalytic HC emission control. The raw emissions from the engine are given in Table 4. Table 4.Emissions from 2.5 Liter DI/TCI+EGR Diesel Auto Engine (European Transient Test Cycle) Mass Emissions (g/km) Test Segment HC NOx CO TPM

Urban (ECE) High Speed (EUDC) Overall (Cycle A)

0.80 0.11 0.36

0.56 0.40 0.46

3.10 0.44 1.41

0.143 0.113 0.124

The catalysts were coated onto 5.66" Dia. x 6" Long (2.47 liters) ceramic substrates with a cell spacing of 400 cpsi. Both Catalyst "C" and Catalyst "D" were evaluated with different platinum loading levels ranging from 2.0 to 45 g/ft3. The test results (% removal) for HC and total particulate (TPM) performance as a fimction of Pt loading are shown in Figure 2a through 2d.

505 (a) Gas Phase HC Removal - ECE Segment

(b) Gas Phase HC Removal- EUDC Segment

1@0

80

a,, '~"""~'-~~:,:m,,_~,-n.................................... 4 0

......

~ "

9- - ' ~ - - -

- -

"

-

-

-

~

.............................

. .................................---~--~aiafy;i-~c.................... 00 ~ 10

,, ~ 20

.........................................................................

, 30

Pt Loading (g/ft3)

, 40

O

0

50

10

20

30

Pt Loading (gift3)

40

60

(d) TPM Removal - Cycle "A"

(c) Gas Phase HC Removal - Cycle "A"

Catalyst "D"

% 3o

'iI

~ a ; y s t

. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

i

0

'C ~ ...........

Catalyst "C"

...............................................................

20

10

,,,

I

i

i

I0

30

40

Pt Loading (glft3)

0

tlO

0

10

20

30

Pt Loading (glft3)

40

liO

Figure 2. - European Transient Test Results for Catalyst "C" and Catalyst "D"Performance for Gas Phase HC and TPM Removal

Figure 2a shows the gas phase HC removal performance for the low temperature (ECE) urban driving segment of the test. The reformulated Catalyst "D" exhibits ca. 80-90% HC removal with a only a slight increase as a function of increasing Pt loading. Catalyst "C" gives lower HC removal levels, between ca. 20% and 40%, again with only a slight increase with increasing Pt loading. The relatively flat behavior of HC removal with increased Pt loading in the low temperature range (100-200~ of the ECE segment of the test indicates that HC adsorption is playing a major role in performance and light-off of the Pt function has not yet been fully attained. Figure 2b gives the HC removal performance in the hotter high speed (EUDC) segment of the test. This shows a clear dependence on Pt loading for both Catalyst "C" and Catalyst "D"and light-off of the Pt appears to be playing

506 the major role in HC conversion for the 200-355~ range. Full light-off appears to be in effect for Pt loading levels of just over 10 g/fi3 for Catalyst "D". Figure 2c shows the HC removal results for Catalyst "C" and Catalyst "D" for the overall Transient Test (Cycle "A") which is the weighted-average of the ECE and EUDC segments. As can be seen Catalyst "D" exhibits very high overall HC removal because of its excellent low temperature performance. Even at the lowest Pt loading level Catalyst "D" gives HC removal levels to meet the EURO II HC+NOx standards with a comfortable margin and comes quite close to the proposed EURO III standards. Figure 2d gives the particulate (TPM) removal of the catalysts over the Transient Test Cycle and it can be seen that high levels of performance (> 40% removal) are attained, especially for the lower Pt loading levels. Overall, these results show that it is possible to achieve good removal and conversion of gas phase HC's and TPM under demanding conditions by the proper choice of base metal oxides and with low levels of platinum on the catalyst.

4. STORAGE AND RELEASE EFFECTS OF EMMISIONS ON DIESEL OXIDATION CATALYSTS

The exhaust temperatures of diesel powered vehicles are quite low at idle and at low speeds and loads encountered in urban driving. To provide effective emissions reductions in normal use, as well as, in tests such as the U.S. FTP and European Transient (Cycle "A"), the catalyst needs to remove SOF and gas phase HC's at temperatures that are many times below precious metal light-off. We have found that the catalyst washcoat which has both storage and oxidation activity will provide the required low temperature removal of SOF and HC's and then at higher temperatures together with the precious metal function convert and oxidized the collected organics. In order to evaluate catalysts for this type of behavior a test was developed to exaggerate the characteristics of the two segments of the European Transient (Cycle "A"). Testing was conducted using a 5.9 liter DlfrCI diesel engine rated at 175 HP and nmning on low sulfur fuel (0.05 wt% S). For gas phase emissions the test involved an extended low load, low temperature (153~ storage period (1 hr.) followed by a rapid ramp to 70% load in only 2 min., a hold for 8 min. and then a step to 100% load and a hold for 8 min. Concentrations of gas phase HC's and CO, at both the catalyst inlet and outlet, along with exhaust flow rates were measured at 1-2 second intervals and thus gas phase emissions could be integrated and totalized over the storage and ramp segments of the test. The results of this test for two samples of Catalyst "D", one with a Pt loading of 2.5 g/fi3 a one with 10 g/ft3 Pt, are given in Table 5.

507 This table gives the test segment, its time interval and the associated maximum catalyst inlet temperature. Also shown are the corresponding % removal of HC and CO. The ramp segment (18 rain. total) is broken down into each of the first 5 one min. intervals and the last 13 min. interval. Also shown is the % removal of HC and CO totalized for the overall storage + ramp segments of the test.

Table 5 Storage and Combustion of Gas Phase HC's by Catalyst "D" (Engine Storage and Ramp Test) % Removal Time Max. Inlet (2.5 g/ft 3) (lo u/fP) Test Segment Interval Temp.(C) HC CO HC Storage 50min. 153 62 -4 65 Ramp

Storage+Ramp

lmin. lmin. lmin. lmin. lmin. 13min. 68rain.

178 255 307 330 344 455

57 -47 -214 -23 50 60-81 52

-2 -16 -51 25 77 84-96 -5

58 -34 -24 63 70 74-77 61

CO 17 15 46 65 82 84 85-93 19

These data indicate that the washcoat and platinum performed different functions over the different temperature ranges of the test. Platinum loading level (2.5 vs 10 g/fl3) had little effect on HC removal below ca. 180~ where HC-storage by the washcoat occurred. Neither was there a significant effect of loading level on HC and CO conversion above ca. 350~ which was well beyond the Pt light-off point for both catalysts. The higher Pt loading; however, did provide significant improvements during the intermediate temperatures in the ramp interval by decreasing HC release and giving a lower CO light-off temperature. It is believed that the results indicate that organic material stored by the catalyst masks the CO conversion sites, so that CO light-off during the ramp occurs only after the sites are burned clean. The lower CO light-off with the higher Pt loading is attributed to more rapid burning of stored HC's. The low temperature storage followed by the rapid ramping to high load represents an extreme but challenging condition for a catalyst and as can be seen some release of gas phase HC's can occur during the ramp segment. However, this can be at least partially alleviated with proper choice of Pt loading level. Furthermore, over the entire storage and ramp cycle the net HC removal remains a net positive 52% or 61%, depending on Pt loading level.

508 For particulate emissions tests simultaneous particulate samples were collected upstream and downstream of the catalyst using two mini-dilution tunnels. In separate tests the time of the low temperature storage segment was varied from 30 to 120 min. and after each storage the ramp to high load was run. The results for inlet versus outlet levels of total particulates and their breakdown into components is shown in Figure 3 as a function of storage time. Particulate Collected (mg)

BaseCat BaseCat BaseCat (30 rain.) (60 rain.) (120 rain.) SOOT

~

SULFATE

SOF

Figure 3 Diesel Engine Storage and Conversion of Particulates As can be seen for each of the storage times (30, 60 and 120 min.) followed by a single rapid ramp to 100% load, there is no release of particulate material from the catalyst outlet relative to the catalyst inlet. In fact catalyst-out levels of particulates are less than catalyst-inlet. Although the gradual increase in baseline particulate levels with longer storage times suggests some holdup of material in the mini-ttmnels, the catalyst-out SOF levels were always less than the inlet levels indicating that the catalyst is active for SOF removal even under these difficult conditions. The distinction between HC and SOF behavior in the tests is attributed to molecular weight differences in these species. The proportion of lighter, gas phase HC released or burned varied with Pt loading (and also with ramp rate). However, the higher molecular weight SOF was held and converted by the washcoat under the most demanding conditions used, and with little or no Pt effect. It is also possible that at least a portion of the gas phase HC's released during the rapid ramp to high load might have come from the breakdown of some of the liquid SOF into lighter gas phase HC-fractions by the catalyst.

509 5. LABORATORY STUDIES OF MODEL SOF ADSORPTION AND COMBUSTION BY DIESEL OXIDATION CATALYSTS

In order to understand the processes occurring during conversion of the soluble organic fraction (SOF) of the particulate emissions by the diesel oxidation catalyst, a laboratory method has been devised that simulates the dynamic adsorption of the SOF by the catalyst and also analyzes the combustion products generated when the SOF is converted. Commercial diesel lubricating oil and diesel fuel were used as models for actual lube and fuel derived SOF. Using a PyranTM-thermal chromatograph, shown schematically in Figure 4, lubricating oil (or diesel fuel) was impregnated on a quartz frit and placed in a quartz sample holder upstream of a small ( 0.25em 3) sample of catalyst coated honeycomb substrate ( 400 cells/in2).

GCMS z~

Gases pass

Trap I

0 z~

After gas analysis, column o cooled to -45 C for temperature programmed GCMS analysis of condensables from trap.

thru GC column to MS

Condensables trapped at-75~ desorbed to GCMS after gas analysis

Catalyst & lube (or fuel) heated to 600~ 10%O2 in He

Figure 4. - Schematic of Pyran TM Thermal Chromatograph System

The lube oil/catalyst assembly was then heated from ambient to 600~ at 10~ in a gas stream containing 10% 02 in He at a flow rate of 40mL/min. As the temperature increased, the lube oil (or fuel) was volatilizes into the gas stream and swept through the catalyst sample. The products exiting the catalyst were then analyzed. Condensable combustion products were trapped cyrogenicaly and the non-condensables were analyzed in real time by a mass spectrometer. Subsequently the condensables were thermally desorbed for analysis by a gas chromatograph-mass spectrometer (GCMS). In separate experiments the by-products exiting the catalyst were analyzed for total hydrocarbons using a flame ionization detector (FID). This allowed determination of the

510

volatilization curves for lube (or fuel) and the effects with or without the catalyst present. The ratio (wt/wt) of lube oil or diesel fuel to catalyst on the honeycomb substrate for the experiments was 0.04 and 0.01, respectively. In diesel exhaust, the SOF to wash coat ratio (wt/wt) is on the order of 0.001. The thermal desorption-GCMS analysis shown in Figure 5 gives a comparison of (a.) chromatograms of SOF desorbed from particulates collected from the exhaust of a diesel engine with (b.) the chromatograms of diesel lube oil and diesel fuel. Superimposed on the chromatograms for calibration are the positions of the corresponding GC retention times for a normal aliphatic hydrocarbon simulated distillation series with different molecular weights. SOF from Diesel Particulates

Abundance -3

A

+ .

o

~

.

.

+

P

X

,~

''

,o

+

.,"

o

"

l0

+tiiL+

.

"~

Diesel Fuel

~

,

,

,

Lube Oil

Time (rain.)

Figure 5. - Thermal Desorption-GCMS Analysis of SOF From Diesel Particulates Compared With Diesel Lube Oil and Diesel Fuel

As can be seen (b.) diesel fuel is composed of fairly distinct components in a range comparable to normal aliphatic hydrocarbons having 12- to 20-carbons. Diesel lube oil, on the other hand, is predominantly a continuum of many compounds with boiling points comparable to normal aliphatic hydrocarbons mainly in the range between 18- and 36-carbon atoms long. The SOF (a.) from particulate emissions collected on a diesel engine, run at low speed and high load, was found to be composed primarily of diesel lube with a small contribution from the higher boiling range of diesel fuel.

511 Figure 6. again shows the particulates collected from the the chromatogram of SOF particulates after the engine (lower curve).

chromatogram of the SOF desorbed fi'om engine exhaust (upper curve) compared with of approximately the same quantity of exhaust had passed through Catalyst "C"

Abundance

J

,,,,~ S O F

Engine-Out

Particulates SOF.

~ ,

,

"--

" I - - ,-

..it ,

ii

1

9

Time

a

Catalyst-Out culates

4o

(rain.)

Figure 6. - Pyran TM Analysis of SOF from Diesel Exhaust Particulates (Engine-Out vs Treated with Catalyst "C") As can be seen treatment of the exhaust by Catalyst "C" results in a dramatic reduction in the SOF of the particulate emissions. The FID traces in Figure 7 compare the total hydrocarbon traces for diesel lube oil as a function of temperature and in a gas stream of either helium (nonoxidizing) or 10% 02 in helium (lean). In the bottom curves it can be seen that with no catalyst present diesel lube vaporizes into either gas stream between 100 and 200~ well below its median simulated

Helium Only

10% 02 in Helium Catalyst

"C"

gamma- Alumina

Lube Oil - No Catalyst J / ~

~ ~ _ _ ~ 1 O0

200

300

400

1~.7.r ..t_.~.~,. ~ '

SO0

Temperature

100

200

390 0

400

800

(C)

Figure 7. - FID Traces of Lube Oil With and Without Catalysts Present

512

distillation boiling point of 430~ With Catalyst "C" present (top curves) and in the absence of oxygen, lube vapors are adsorbed by the catalyst and no hydrocarbons are released below 200~ Those that are released are of a lesser amount. In the "lean" gas stream virtually no hydrocarbons pass through Catalyst "C" at any temperature. By comparison a honeycomb substrate coated with high surface area gamma-alumina does not adsorb and hold lube oil very effectively in the nonoxidizing gas stream (middle curves). In the "lean" gas stream gamma-alumina adsorbs and holds the lube oil better, but not as well as Catalyst "C". Volatilization and adsorption of lube oil by the catalysts is followed by catalytic oxidation to CO2 at higher temperatures as is shown in Figure 8. In the PyranrM-GCMS experiments, CO2 is the only non-condensable oxidation product measured from the combustion of lube oil in the "lean" gas stream by either Catalyst "C" or the gamma-alumina. The onset of COz evolution with Catalyst "C" occurs at approximately 180~ which is just above the temperature range for the lube oil volatilization curve which is also shown. Lube conversion to CO2 is virtually complete with Catalyst "C" as determined by CO, mass balance (95-100%) and the absence of detectable condensable species. Abundance ~

COnvolution Catalyst "C"

Lube

9

4

II

lip 0 Time (min.)

tit

14

Ill

lid ...........

Figure 8. - Conversion o f Lube Oil to CO~ by Catalysts

Gamma-alumina by comparison begins to combust lube oil to CO2 at approximately 300~ which is well above the temperature of lube oil volatilization the combustion onset temperature for Catalyst "C". Furthermore, gamma-alumina typically converted only 40 to 50% of the lube to COz.

513

Diesel fuel was fotmd to volatilize approximately 50~ lower than lube oil. This was accompanied by a corresponding slfift to lower combustion temperatures with Catalyst "C" (Figure. 9). Fuel conversion with Catalyst "C"was typically 80% by mass balance, with CO2 the only noncondensable product. In contrast to the onset of fuel combustion shifthag to lower temperatures over Catalyst "C", the onset of fuel combustion over altunina was at higher temperature and occurred at almost the same temperatm'e as did lube oil combustion. Abundance

9

4

II

9

tO

Time (rain.)

III

14

III

III

Figure 9. The Volatilization of Diesel Fuel and Its Combustion by Catalysts Non-burned filel hydrocarbons were observed in the product stream with both Catalyst "C" and gamma-alumina. However, the molecular weight distributions were quite different (Figure 10). Catalyst "C" combusts all the heavier fuel hydrocarbons, with Olfly the lightest fuel species bypassing the catalyst, while the entire molecular weight spectrum of the fuel is observed in the non-burned hydrocarbons from the gammaalumina catalyst. These data suggest that while both Catalyst "C" and gamma-ahunina adsorb SOF components at low temperatures and btm~ them as the temperature increases, each catalyst's mechalfism of adsorption and subsequent combustion is quite different. With Catalyst "C", the light-off temperature is an apparent function of the volatility of the SOF component. Catalyst light off occurs when the temperature is lfigh enough for the adsorbed component to desorb from the catalyst surface: 150~ for the fuel component, and 200~ for the lube. The observed difference in light-off

514

temperature between the fuel and lube for Catalyst "C" is due to the difference in the lube and fuel volatility. Chromatogram of Dieeel Fuel

Abundance 0

-

-U

Unburned

-

o G

Fuel

o a

Species

TI~

-

Catalyet

~

0

"C"

IIIn.I

Figure 10. - Chromatograms of Diesel Fuel and Unburned Fuel Fractions from Catalyst "C" and Gamma-Alumina However, the catalyst is not hot enough to burn the fuel's lowest molecular weight fraction in these experiments. These components are not adsorbed by Catalyst "C", and pass over the catalyst at temperatures below the catalyst light off temperature. The contrast with gamma-alumina is striking. Gamma-ahunina lights off at 300~ 100~ higher than does Catalyst "C", and at approximately the same temperature for both the diesel fuel and lube, independent of the components' volatility. This suggests that the alumina is forming similar intermediate speeies on its surface from the adsorbed lube or fuel SOF components. Gamma-alumina has lower conversions for both the fuel and lube than does Catalyst "C" because the alumina catalyst adsorbs less of each SOF component and the adsorbed species desorb from the alumina catalyst surface before the lightoff temperature is reached.

6.SUMMARY AND CONCLUSIONS

Diesel oxidation catalyst technology using base metal oxides in the washcoat for removal and conversion of particulate SOF and gas phase HC's has been demonstrated in steady state and transient engine tests.

515 These active washcoats have been fotmd to adsorb emissions at low exhaust temperatures and oxidize them at higher temperatures in the engine duty cycle. Precious metal in the form of low loading levels of platinum can also be incorporated into the catalysts for additional gas phase HC activity and for CO conversion. By proper choice of catalyst oxides in the washcoat the technology can be tailored for current U.S. truck applications which require particulate emission reduction or by modification include improved gas phase HC removal and conversion, especially at low exhaust temperatures. This gives catalyst technology to address the needs for European diesel auto emissions standards. Engine storage and release experiments show that adsorption of emissions (HC, SOF) can occur on a catalyst under extended low load, low temperature conditions. Under subsequent rapid ramping to high load and temperature in a matter of minutes reemission of gas phase HC's can be controlled fairly effectively with as little as ca. 10 g/t~3 platinum. Storage and release tests show that the catalyst is very effective for controlling SOF emissions and catalyst-out SOF is consistently lower than engine-out baseline levels. A laboratory test was developed to investigate the mechanisms of adsorption and conversion of SOF on diesel catalysts. This test used diesel lube oil and diesel fuel as models for SOF. Test results have shown that SOF components are adsorbed effectively by the catalyst at temperatures below ca. 200~ and then fully oxidized by the catalyst washcoat at temperatures above about 200~ This behavior is consistent with what has been seen in engine tests.

RERERENCES

1 P. Zelenka, W. Kriegler, P. Herzog and W.P. Cartellieri, "Ways Toward the Clean Heavy-Duty Diesel," SAE No. 900602 (1990). 2 J.S. McArragher, et al.,"Motor Vehicle Emission Regulations and Fuel Specifications - 1992 Update," CONCAWE, Brussels (1992) 111. 3 R.J. Farrauto, K.E. Voss and R.M. Heck, SAE No. 932720. 4 K.E. Voss, B.O. Yavuz, C. Hirt and R.J. Farrauto, SAE 940239.


A. F rennet and J.-M. Bastin (Eds.) Catalysis and Automotive Pollution Control 111 Studies in Surface Science and Catalysis, Vol. 96 9 1995 Elsevier Science B.V. All rights reserved.

517

PERFORMANCE OF OXIDATION CATALYSTS FOR HEAVY-DUTY DIESEL ENGINES

H. J. Steina, G. H0thwohlb and G. Lepperhoffb aMercedes-Benz AG, Dept. EN/MGA, D-70322 Stuttgart, Mail Code T 352, Germany bFEVMotorentechnik GmbH & Co. KG, Neuenhofstrasse 181, D-52078 Aachen, Germany

ABSTRACT A variety of catalyst substrates, washcoats, and formulations were screened on a Mercedes OM 366 LA direct injection, turbocharged-intercooled engine in order to identify the optimal engine/catalyst combination for US applications. The engine was operated at five steady state modes, and on the US transient and European 13-mode cycles. The carbon monoxide (CO) and hydrocarbons (HC) light-off temperatures were lowest for catalysts with a high platinum loading and an active washcoat, slightly higher for catalysts with low platinum loadings, and considerably higher for the palladium catalyst. The particulate (PM) emission at light load operation with an exhaust gas temperature about 423 K was reduced by 75 % to 85 % with all catalysts due to the high conversion rate of the PM soluble organic fraction. The PM efficiency still increased by 5 % at medium load operation, and then started to decrease around a temperature of 550 K due to the beginning of sulfate formation. Therefore, TWC technology cannot be used for Diesel engines. The sulfate formation could be minimized by a higher space velocity, an optimized washcoat, and a lower platinum loading, or palladium loading, respectively. On the US transient cycle, PM was reduced by 20 % to 35 % with all catalysts tested. Among the two catalysts with 35 % efficiency, catalyst D which produced less sulfate at high temperatures was selected as first choice. Deterioration of catalyst D over 2200 hours was 8 % for PM, 13 % for CO and 21% for HC. On the 13-mode cycle, PM increased by 100 % to 350 % due to a considerable sulfate formation at the highly weighted high power modes. Since the SOF fraction of the particulates is less pronounced in this cycle, the potential of an oxidation catalyst for PM removal is limited.

518 1. INTRODUCTION Stringent emission standards for heavy-duty Diesel engines will require in the near future significant reductions of the oxides of nitrogen (NOx) and particulate (PM) emissions. To a high degree, modification of the engine and the introduction of a low sulfur Diesel fuel will contribute to reaching this goal. For some applications, however, the use of at~ertreatment technologies is necessary for passing the 1994 PM standard in the USA with a sufficient safety margin. Since particulate filtering systems proved to be too complicated and expensive for the OM 366 LA engine, flow through oxidation catalysts were considered as a viable solution [1]. Such systems have already been successfully introduced for passenger car Diesel engines, and transfer of the technology to truck engines seemed to be a feasible way. The OM 366 LA is a turbocharged and intercooled direct injection six cylinder in-line engine with a swept volume of 5,9 dm 3, and is offered for the US market in four power versions of 127, 142, 157 and 172 kW. In this program, a 172 kW prototype engine that did not yet meet the 1994 PM emission limits was used to select the optimal converter configuration.

1.1. Particulate composition Diesel particulates (PM) are collected on a teflon-coated glass fiber filter after dilution of the raw exhaust gas with clean ambient air in a dilution tunnel to a temperature at or below 395 K [2]. The dilution process changes the particle characteristics significantly. In the raw exhaust gas at high exhaust gas temperatures, the particles mainly consist of soot (carbon), the so called insoluble fraction (Insol). Through the dilution and cooling process, part of the high boiling exhaust hydrocarbons from the fuel and lubricating oil of the engine will condense and/or adsorb onto the soot forming the Soluble Organic Fraction (SOF) [3]. Additionally, sulfates (SO4) out of the fuel sulfur will condense onto the carbon core. Depending on the water content of the particulate weighing chamber, the sulfate is usually associated with 1,3 g to 2 g water per gram of sulfate [4]. A typical PM profile of the OM 366 LA on the US transient cycle is shown in Figure 1. Oxidation catalysts are able to oxidize HC, CO and the SOF portion of the particulates, but will nearly not affect their Insol portion nor the NOx emission. The efficiency depends on the catalyst formulation and on the converter size. A major problem associated with the use of oxidation catalysts for Diesel engines is the possible oxidation of SO2. Depending on the catalyst efficiency, this can considerably increase the sulfate portion of the particulates, and thus the total PM [5].

519 Sulfate + Water F

SOF Oil

sol

Figure 1 Typical particulate composition of the OM 366 LA on the US transient cycle

1.2. Catalyst selection The catalysts evaluated in this program are listed in Table 1. Both ceramic and metallic monolith substrates with a diameter of 266 ~mn were used. The lengths of the substrates were 152 nun and 76 lnln resulting in a catalyst volume of 8,6 din 3 and 4,3 dm 3, respectively. The precious metal catalyst formulation comprised Platinum (Pt) mad Palladium (Pd) with various loadings. Catalyst A* was only tested for a comparison of the ceramic vs. metallic substrates using identical catalyst formulation and converter size. Before running the test program, all catalysts were aged 50 hours at high temperature conditions. Table 1 List of catalysts Cataly st

Material Cell density Cells/cm 2 46 (~eramic Metallic 23 Ceramic 46 Ceramic 62 Ceramic 62 Metallic 23 Ceramic 62 ,,,

A A* B C D

E F

Coating Metal Platinum (Pt) Platinum (Pt) Platinum (Pt) Platinum (Pt) Platinum (Pt) Palladium (Pd) Platinum (Pt)

,.

g/din 3 1,77 1,77 1,77 0,35 0,07 1.77 0,02

Space Velocity 95140 95140 190280 95140 95140 95140 95140

.....

520 1.3 Test program

First, the catalysts were screened on five engine modes, as shown in Table 2. The catalyst screening was performed with three basic viewpoints. First, the influence of the substrate material (ceramic or metallic) was evaluated using catalysts A and A*, since it affected the design of the test program. Second, the influence of the space velocity was evaluated by comparing catalysts A and B with identical loadings, but different size. Third, optimized catalyst coatings were specifically tested for PM removal, comprising a reduced Pt content (0.35, 0.07 and 0,02 g/dm 3) and a Pd coating of 1,77 g/dm 3. The result of the screening procedure was used to select a number of catalysts for further testing on the two most important official exhaust test cycles: the US transient cycle and the European 13-mode cycle. This part of the program consisted of verifying the conclusions from the screening procedure on these cycles. On the transient cycle, the engine is mainly operated under light or medium load conditions, whereas on the 13-mode cycle high load operation is predominant [6]. PM was measured in a fidl flow dilution tmmel, and was analyzed for SOF and sulfate.

Table 2 Engine modes for catalyst screening Mode

2 3 4

Engine speed s- 1 15 26 26 26 26

rain- 1 910 1560 1560 1560 1560

Engine Torque Nm 90 83 208 415 625

Power kW 8,6 13,6 34,0 67,8 102,1

Catalyst temperature K ~ 423 150 458 185 548 275 673 400 753 480

521 100 Efficiency [%] 80 60 40 20

_

. . . . . . . . . . . . . . . . .

80-

.

.

.

.

20-

~s

.~

................ ~..~...............................................................

40

600

500

700

80

400 500 Efficiency [%] 100

Efficiency [%]

!!!!

700

800

60 40 20

500

600

700

.

- - ~ ......................

-300 ..................................................................~ - -.............. ~

.4oo ....211111111111111111111111111111111111111111111111111111111 ,~ ......... 600 700 Temperature [K]

Cat A

.

.

.

.

.

.

.

.

.

.

.

.

.

.

c o

...............................

-I/ 500

600

700

800

"" Efficiency [%]]

........................................................

500

.

0 400

800

Efficiency [%]

-500 400

600

80

...........

-100 .................................................~-~-............................

-100J

iiii~" ........

-200J

:::::::::::::::::::::

pM

-300J

i :4,oooo1

800

400

2111 500 600 700 Temperature [K]

I

~--

- - - - CatA* I

Figure2 Influence of the reactor material on the catalyst efficiency

2.

..........

60 .......................-~-~ ..............................................

.............................................................................

-200

~

20 ....~ 1 ........................................................................

400 100

.......................................... ' ~ ~ ~ ~ ~ . _ . ~~

80

..............~---~(o--6040-

Efficiency [%]

. . . . . . . . . .

!!}!

400 100

. . . . . . .

100

CatA----

80

CatB ]

Figure3 Influence of the space velocity on the catalyst efficiency

EVALUATION OF CATALYST PERFORMANCE

2.1. Catalyst substrate Catalyst A was prepared on a 46 cells/cm 2 ceramic monolith. It is based upon a washcoat optimized for Diesel engine operation, but with the usual Pt content of 1,77 g/dm 3. Catalyst A* had a washcoat and a precious metal kind and loading

522 identical to catalyst A, but was prepared on a 23 cells/cm2 metallic monolith. Due to the slotted structure of the metallic substrate, the nominal cell density is equivalent to the cell density of the ceramic substrate. As shown in Figure 2, the catalyst efficiencies are very similar for the three components HC, CO, and PM. The efficiency for the gaseous components HC and CO is less than 20 % at a temperature of 420 K, then rapidly increases with increasing temperature reaching the maximum of 98 % at 500 K for CO and of 80 % at 550 K for HC. For PM, the trend is opposite: the PM removal of 95 % at low temperatures decreases with increasing temperature, and is then followed by an increase of PM at high temperatures due to the formation of sulfate. Since no significant difference between the two substrates was found, a ceramic substrate was used in most of the following program because of the cost advantage in mass production.

2.2. Space velocity Catalyst B was identical to catalyst A, but only half that long. Therefore, the space velocity was twice as high, and the reaction time on the catalyst surface reduced. The results are shown in Figure 3. While the space velocity has only a minor influence on the CO efficiency at low temperatm'es only, HC and PM efficiencies are highly affected over the whole temperature range. The HC efficiency is 10 % to 20 % lower with the higher space velocity . For PM, the higher space velocity leads to a lower efficiency at low temperatures due to a reduced SOF removal. However, at high temperatures there is less PM increase due to a reduced sulfate formation. In total, reduction of the catalyst size is not satisfactory: on one hand, PM formation at high temperatures is still considerable, on the other hand the poor SOF efficiency is not sufficient for effective PM removal, and the poor HC efficiency might cause partial oxidation of hydrocarbons which often coincides with odor formation.

2.3. Precious metal loading So far, it was found that the substrate had only a minor influence on the catalyst efficiency, and that reduction of the catalyst size was disadvantageous, in general. As a consequence, the precious metal loading was changed: the Pt content was reduced to 0,35 g/din~ (catalyst C) and to 0,07 g/din~ (catalyst D). In another formulation, Pd was used instead of Pt (catalyst E), since Pd catalysts are less likely to form sulfates by direct oxidation [5]. For the gaseous emissions HC and CO, the results are shown in Figure 4. The HC efficiency of the two Pt formulations is similar to that of the highly active catalyst A (see Figure 2). It reaches the maximum around 550 K, but with a better low temperature activity of catalyst C. The Pd catalyst has a poor HC conversion at low temperatures, and reaches the maximum conversion rate not before 700 K.

523

100

Efficiency [%]

100 Efficiency [%] ,.

80 ............................. ~ , - : ; ; , ~ ~ ' : - - - ......... .-1 ;~':"~-~ ........... 60

..........

60~ ....................-~/'- .......................-/.-S- ...............................

~,..-t"

40 ....... ~ " / t

HC ................)," ................................................

20 ..... ~/ . ~ ,".

~,.-.~i .........................................................

0 400

500

600

700

4 0 + ...................I I

.......................

-.~ . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

~0~............../ , , .................;-' ..................co ................ 0 [~ J ~

............../

-20 400

800

.................................................

*% ~~ "" 500

Temperature [K]

600

700

80

Temperature [K] ~-

Figure 4 efficiency

_

Cat C - - - - Cat D . . . .

Cat E

Influence of the precious metal loading on the gaseous emissions

Above 700 K, the activity of the three catalysts is very similar. These findings also apply to the CO conversion, but with a lesser difference between the two Pt formulations over the whole temperature range. 0,5 0,4 0,3 0,2 0,1

g/kWh .............................................................1 ~ ] ~

Sulfate~

SOF

~Insol

1....

!!!!!!!!!!!!!! !!!!!!!!!!!!!!! !!!!!!!!!!!!!! !!!!!!!!!!!!!!! !!!!!!! 1245 Engine Out

1245 Cat C

Model'423K

1245 Cat D

1245 Cat E

1245 Cat F

Mode 2" 458K Mode 4" 673K Mode 5" 753K .

.

.

.

.

.

.

.

]

.

Figure 5 Influence of the precious metal loading on the PM level and on the particulate composition For PM, the particulate composition is crucial in assessing the catalyst efficiency. Figure 5 exhibits the PM emission with and without catalysts at the engine modes 1, 2, 4 and 5 and broken into the respective Insol, SOF and sulfate/water fractions. An additional formulation (catalyst F) was considered in this comparison. Catalyst F is identical to catalyst D, but with a fi~her reduced

524 Pt content of 0,02 g/dm 3. At the two low temperature modes, the SOF fraction of the particulates is high. All Pt catalysts (C, D, F) are very effective in removing SOF at low temperatures, but much less effective at high temperatures. With the Pd formulation (E), the overall SOF efficiency is slightly lower. This counteroriented trend of the conversion of the particulate (SOF) hydrocarbons compared to the gaseous (HC) hydrocarbons (see Figure 4) is also seen with the highly active catalyst A, and points to a different reaction mechanism [7]. The gaseous hydrocarbons are oxidized directly through contact with the catalytically active surface, and the efficiency therefore increases with increasing temperature. With all catalysts, some storage of the insoluble carbon fraction was observed at the modes 1 and 2. At low temperatures, a large portion of the SOF is adsorbed onto this accumulated soot layer leading to sticky particles which remain on the washcoat. With increasing temperature, the SOF hydrocarbons are oxidized leaving back dried particles. The majority of these particles is blown out with increasing exhaust gas flow. However, a small part of the soot is oxidized in the catalyst. At high temperatures, the particulates pass through the converter nearly tmchanged. No adsorption of SOF can take place, and the SOF efficiency decreases. At the high temperature mode 5, sulfate formation is considerable with all formulations. The most sulfate production is observed with the highest Pt content of catalyst C, the least with the lowest Pt content of catalyst F. Sulfate formation of Catalyst D with 0,07 g/dm 3 Pt is similar to that of catalyst E with 1,77 g/dm 3 Pd. From that it can be concluded that there is a direct relationship between sulfate formation and precious metal loading and formulation. These results clearly point to the strategy of finding the optimal catalyst selection. SOF removal, the catalyst's only way of reducing PM, is largely independent of precious metal content or choice. Contrary to that, sulfate formation, which in turn increases the total PM emission, is retarded with lower Pt loadings or with Pd catalysts. The gaseous components HC and CO are effectively oxidized at low temperatures only with high Pt loadings. Since Diesel engines have inherent low HC and CO emissions, a catalyst is not required for passing even the strictest emission limits. Overall, the best solution is therefore a catalyst with a low Pt loading. This catalyst combines a high SOF removal potential with the low sulfate formation potential usually associated with a Pd catalyst, without compromising too much the efficiency of the gaseous components, like the Pd catalyst.

525 1,

Relative Emission [%]

Engine Out [~

Figure 6

Cat C Sulfate ~

Cat D SOF

1

Cat E

Cat F

Insol

P M emissions on the US transient cycle

3. CATALYST VERIFICATION

3.1. US transient cycle The US transient cycle is light to medium load cycle where the engine is operated mainly in the idle and rated speed regimes. The average load factor accounts for only 20 %. The maximum temperature during the cycle does not exceed 670 K, and the average temperature is around 490 K. Therefore, the potential for unwanted sulfate formation is limited. In Figure 6, the PM engine out level of the prototype engine is set to 100 %. With all catalysts, total PM is reduced between 20 % and 35 % due to a high SOF conversion. The Pt content does not significantly influence the SOF efficiency, but the efficiency is lower with the Pd catalyst E. As expected, no sulfate formation is observed. In total, an oxidation catalyst is an effective means for reducing the PM emission to a level that is well below the 1994 PM emission standards. Based on the above results, catalyst D was selected as first choice. Compared to catalyst C, the high temperature behaviour, i.e. sulfate formation is better due to the lower Pt content, although this is basically not needed on the US transient cycle. Furthermore, the lower Pt content is also connected with a lower catalyst price. The very low Pt content of catalyst F was not considered necessary for the US engine application. Such a low Pt loading is also critical with regard to catalyst ageing, a very important factor in the certification process of engines for the US market.

526

3.2. European 13-mode cycle The 13-mode cycle is a steady state cycle with a large portion of full load engine operation. The average load factor is about 45 %. The maximtma temperature reaches more than 850 K, and due to the steady state conditions the catalyst is subjected to these high temperatures for an extended period of time. Compared to the conditions of the transient cycle, the SOF portion of the particulates is smaller, and there is a high potential for sulfate formation. Relative Emission [%] 400-r 300 200 100

Engine Out

Cat C I ~ ] ~ Sulfate ~

Figure 7

Cat D SOF

Cat E ll

Cat F

Insol

PM emission on the 13-mode cycle

Figure 7 shows that the PM level with catalyst is higher by a factor of 2 to 3,5 than the engine out level. Even with the very low Pt content of catalyst F, the Euro 2 PM standard is by far exceeded. This is caused by a dramatic increase of the sulfate fraction. The SOF fraction is lower than on the US transient cycle, and due to the high temperatures SOF efficiency is poor. Thus, it can be concluded that a catalyst for European applications will be smaller in size (higher space velocity will reduce sulfate formation) and very limited in its overall efficiency on the 13-mode cycle. Such a catalyst was not tested in this program, since the investigation was only aimed to developing a US version.

4. DURABILITY

TESTING

Catalyst D was tested in durability program over a total time of 1600 hours ( = 640 durability cycles) which corresponds to 213.000 km of field operation. The durability cycle consisted of four different full load modes at 2300, 1380, 950, and 2600 min-1. The first mode was run for one hour, the other modes for 0,5

527

hours, each. The emissions were measured every 400 hours, mid the four measuring points subjected to a linear regression analysis. T1-.e regression line was then extrapolated to the 2200 hours endpoint of the durability run. This endpoint corresponds to 296.000 km of field operation, which is defined in the regulations as the "useful life" of the OM 366 LA engine. By definition, the deterioration factor is the difference between the starting point and the endpoint of the regression line. For the certification of an engine, the emissions values must be multiplied with the individual deterioration factors. From that it is clear that low deterioration factors are very important. 1,4

Deterioration Factor l,

1

,

2

-

Deterioration Factor

1,4

~

1

~ 2

..............................................................................................

1~

11 ............................................................................................

~

............................ i

.

0,8 ............ l _.//_ HC ..4.. CO I.............................. 0,6 ..............................................................................................

0

0,4

0,4

0

400

Figure 8

800 1200 1600 Operating Hours

2000

~ 6

.

.

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..............................................................................................

0

400

800 1200 1600 Operating Hours

2000

Influence of catalyst ageing on the HC, CO and PM emissions

The results are shown in Figure 8. The zero hour emissions values are set to 1, and the other values are related to the zero hour values. The deterioration factors for the gaseous components HC and CO are 1,21 and 1,13, respectively. Since both emissions are far below the respective emission standards, these values are acceptable, especially with regard to the low Pt loading. The PM emission is nearly constant over the whole durability nm which results in a deterioration factor of 1,08. This value is low enough for the engine to comply with the PM standard. It also demonstrates that advanced catalyst teclmology, i.e. low precious metal loadings can be applied to heavy duty Diesel engines over their useful life period. Apart from the catalyst evaluation in this program, a slight decrease of the NOx emission was observed in the durability run of the engine.

528 REFERENCES

J. Widdershoven, F. Pischinger, G. Lepperhoff et al., Possibilities of Particle Reduction for Diesel Engines, SAE 860013, Detroit, 1986 Code of Federal Regulations, Title 40, Part 86, Subpart N, Emission Regulations for New Gasoline- and Diesel-Fueled Heavy Duty Engines S. Reichel, F. Pischinger, G. Lepperhoff, Influence on Particles in Diluted Diesel Engine Exhaust Gas, SAE 831333, Detroit, 1983 J.C. Wall, S.A. Shimpi, M.L. Yu, Fuel Sulfur Reduction for Control of Diesel Particulate Emissions, SAE 872139, Detroit, 1987 5 M.G. Henk, W.B. Williamson, R.G. Silver, Diesel Catalysts for Low Particulate and Low Sulfate Emissions, SAE 920368, Detroit, 1992 G.M. Cometti, K. Klein, G.J. Fr~akle, H.J. Stein, US Transient Cycle Versus ECE R 49 13-Mode Cycle, SAE 880715, Detroit, 1988 D.J. Ball, R.G. Stack, Catalyst Considerations for Diesel Engines, SAE 902110, Detroit, 1990

A. F rennet and J.-M. Bastin (Eds.) Catalysis and Automotive Pollution Control 111 Studies in Surface Science and Catalysis, Vol. 96 1995 Elsevier Science B.V.

CATALYTIC

REDUCTION OF NITROGEN DIESEL EXHAUST GAS

529

OXIDES IN

B. H. E n g l e r , J. Leyrer, E. S. L o x a n d K. O s t g a t h e

Degussa AG, Hanau, Germany ABSTRACT This paper reports first results of research and development work to achieve nitrogen oxide reduction under lean diesel exhaust gas conditions. Much attention is paid to the influence of operation conditions on catalyst performance. A major part of the paper deals with the influence of the hydrocarbon component, the hydrocarbon concentration and the HC/NO ratio on the activity of a special developed platinum based catalyst. Other aspects discussed are a spectroscopic characterization and a selectivity study. A hypothesis of a "dual-site" reaction mechanism for NOx-reduction in lean diesel exhaust gas precious metal based catalyst is established. Finally, first promising results on the performance of the catalyst system in a vehicle dynamometer test are given.

1. INTRODUCTION

Due to current and proposed legislation in Europe and the United States there is a growing need for low-emission diesel passenger cars and trucks. Main emphasis is put on diesel engines with limited emission of nitrogen oxides and particulate matter as well as gaseous hydrocarbons and carbon monoxide. Various catalytic aftertreatment teclmiques are available to reduce those pollutants from the exhaust gas of on-road diesel vehicles, which are the flowthrough diesel oxidation catalyst [1-4] and the particulate trap [5-6]. Whereas the diesel oxidation catalyst is a well accepted technology to limit particulate, hydrocarbon and carbon monoxide emissions in the exhaust gas of passenger cars in Europe and of light and heavy duty trucks in the US, the catalytic diesel trap is still lacking a reliable regeneration teclmology. A major challenge left is the removal of NOx from the oxygen rich exhaust gas of diesel engines. One possibility is the use of an exhaust gas recirculation system (EGR). But it is well

530

known that EGR systems, while lowering the tailpipe NOx emission, could increase the particulate emission [7]. Also the feasibility of the use of catalysts is discussed in the literature. Unfortunately, conventional precious metal containing three-way type catalysts do not convert nitrogen oxides under excess of oxygen [8]. With the selective catalytic reduction process by using ammonia as reducing agent, NOx emission can be reduced under diesel engine exhaust gas conditions [9], but the use of nitrogen containing substances like ammonia or urea, makes this process difficult to apply to on-road vehicles, especially passenger cars. Several laboratory investigations have been reported on the catalytic removal of nitrogen oxides from oxygen-rich exhaust gases without the addition of nitrogen containing substances. Direct nitric oxide decomposition would be the preferred method, but the catalytic activity of the best current technology is very limited under typical diesel exhaust gas conditions [10]. Hence, there is much interest in the reduction of nitrogen oxides by adding CO [ 11 ], hydrocarbons [ 1217] or alcohols [18] to the exhaust gas stream. In a recent paper [19] first results were described of an investigation to achieve NOx reduction in diesel exhaust gas by using special coated, zeolite type catalyst. The infuence of the type of gaseous HC-components, HC-concentration, sulfur dioxide, carbon monoxide, water and oxygen content as well as space velocity on catalytic activity was discussed. This paper describes further investigations on this subject. Different parameters affecting the performance and particularities to the use of this system in modem diesel engines are discussed. 2.

SELECTIVITY

VERSUS

SPACE

TIME

ANALYSIS

OF

INTEGRAL

REACTOR

CONVERSION DATA- A TOOL TO IDENTIFY REACTION PATHS

In the literature several reaction mechanisms are discussed for the reduction of nitrogen oxides by hydrocarbons under excess of oxygen with precious metal free catalysts [13,16-20]. For precious metal containing catalysts only a few reference data exist. The majority of the investigations use the measurement of reaction intermediates by spectroscopic teclmiques to determine the reaction path [20]. Another way, used in this study is the use of a selectivity analysis [21-22]. For a given reaction the conversion and selectivity of the reactants can be calculated by following equations:

531 A

Reaction:

~

B

(1)

Conversion: FAO XA

---

-

FA _

FAO F e ....

FA~

Moles of A disappeared Moles of A fed

Moles of B formed Moles of A fed

(2) (3)

with = Conversion of reactaa~t A = Conversion of product B XB = Molar flow of reactant A and product B [mol/s] FA and F B = Molar flow of reactant A at reactor inlet [mol/s] FAO XA

Selectivity: SB = X B

XA

= Moles of A converted to B Moles of A converted

with

SB

=

(4)

Selectivity for product B

From these data the initial selectivity SB o can be determined by the following equation:

~176 I Vll

SBO- lim

1 .!FB.d

with: SBO FB V V/FAo

= = = =

Initial selectivity for product B Reaction rate of B [mol/kg 9s] Catalyst volume [1] Space time [1. s/mol] = Residence time of reactant A = Inverse space velocity

(5)

532 This integration is best carried out graphically by plotting SB against V/FAo. From these data the identification of the reaction paths is possible by calculation of initial selectivity for different reaction products. The interpretation is summarized in Table 1.

Table 1" Theory and interpretation of the selectivity study Reaction

First derivation

Initial Selectivity

A --> B

SB o =

dS.

1

~ = 0 d

dS.

B

A

SB o + SCO = C

A

---> B

V

---> C

1

~ ~ 0 d

V

1

dSB

SC ~ = 0

d V

SB o =

o o

3.EXPERIMENTAL 3.1 C a t a l y s t

The monolithic samples were prepared by coating cordierite honeycombs (cell density 62 cells/cm2; wall thickness 20 ~tm) with an aqueous slurry of the desired washcoat oxide. After drying and subsequent calcination at 530~ for 2 h in air, the washcoated supports were impregnated with an aqueous solution of the platinum salt, dried and activated in hydrogen for 2h at 530~ The total platinum loading was fixed at 50 g/ft 3 Pt. For model gas experiments samples with a diameter of 2.5 em and a length of 7.6 cm were used. The vehicle test results were obtained with full size substrates with a diameter of 14.4 cm and a length of 15.2 cm.

533 3.2 Performance Tests The majority of the performance tests were done with an integral model gas reactor, described in a recent paper [2]. It consists of a gas mixing section, a reactor section and an analytical section. For simulation of typical diesel exhaust gas hydrocarbons several selected liquid HC-components were introduced in the exhaust gas stream by means of an HPLC-pump (Shimazu LC9A) and using an stainless steel evaporator (T>180~ The model gas compositions used in this study are given in Table 2.

Table 2: Model gas compositions and test procedures

CO [ppm] H 2 [ppm] HC [ppmC1] NO [ppm] SO2 [ppm] 0 2 [vol.-%] CO 2 [vol.-%] H20 [vol.-%] N 2 [vol.-%] Space Velocity

[Nml]

Test 1 350 117 3200 270 25 6 10.7 10 balance

Test 2 350 117 3200 270 25 6 10.7 10 balance

50.000

50.000

Test 3 Test 4 350 350 117 117 800-12800 3200 270 100-800 25 25 6 6 10.7 10.7 10 10 balance balance 50,000

50.000

Test 5 350 117 3200 270 25 6 10.7 10 balance 20.000100.000

125-500 125-500 125-500 125-500 125-500 Temperature 500-125 range [~ Test 1: HC-component: n-Hexadecane (C 16H34) Test 2: HC-component: Methane (CH4), Ethane (C2H6), Propane (C3H8), Butane (C4H 10), n-Heptane (C7H16), Iso-octane [= 2,2,4 Trimethyl-pentane] (C8H18), n-Hexadecane (C 16H34), Ethylene (C2H4), Propylene (C3H6), 1Butylene (C4H8),1-Octene (C8H16), Methanol (CH3OH), Ethanol (C2H5OH), 1-Propanol (C3H7OH), 1-Butanol (C4H9OH), Toluene (C7H8), 1-Methylnapthalene (C 11H10), ortho-, meta-, para-Xylene (C8H10) Test 3-5: HC-component: n-Hexadecane (C 16H34) The liquid hydrocarbons n-hexadecane (cetane number = 100) and 1methylnapthalene (cetane number =0) were chosen as model components to simulate diesel fuel, the hydrocarbons iso-octane (octane number = 100) and nheptane (octane number = 0) as model components to simulate gasoline, respectively.

534 On-line analysis was perfonned for the hydrocarbons by a flame ioniziation detector, for CO, N20 and CO2 by NDIR-detectors, for NO, NO2 and NOx by a chemuluminescence detector and for 02 by a paramagnetic detector. Except for the 02 detector, all sample lines were heated to > 120~ to avoid condensation of the exhaust gas components. The amount of N2 formed by the reaction was calculated from the mass balance. A detailed list of the on-line analyzers used is given in Table 3.

Table 3: List of on-line analysis methods Component HC CO CO 2 N20 NOx, NO, NO2 02

Detector FID NDIR NDIR NDIR Chemiluminescence Paramagnetic

Type Ratfisch RS 55 HC Leybold Binos 100 Leybold Binos 100 Leybold Binos 100 Tecan CLD 700 EL Siemens Oximat

Final test results were performed on a chassis dynamometer according to the European MVEG-A test procedure. The passenger car used had a inertia weight of 1500 kg and was equipped with a 2.5 1 DI/TC four cylinder diesel engine.

3.3 Aging Procedure All samples were measured in fresh or diesel engine aged conditions. The stationary diesel engine bench was equipped with a 1.9 1 IDI/TC diesel engine described in a recent paper [1 ]. Table 4 describes the 50h aging cycle used in this

Table 4" Diesel bench aging cycle for NOx-catalyst (1.9 1 IDI/TC diesel engine;diesel fuel S-content: 0.15 wt.-% S; lubricating oil phosphorous content: 0.1 wt.-% P; duration 5Oh) [19] Step

Engine Speed [rpm]

Load [Nm]

Duration [min]

Converter Inlet Temperature

[oc]

1 2 3 4 5

2000 3000 4000 4000 Repeat step 1-4

50 115 10 110

18 6 6 30

250 465 290 620

535 study. This cycle was chosen to give a first indication of the long term stability of the catalyst. The aging cycle includes low temperature conditions as well as high temperature phases. The diesel fuel used contained 0.15 wt.-% sulfur, the lubricating oil had 0.1 wt.-% phosphorous. The cetane number, density and all other specifications correspond to the German standard DIN 51601 for automotive diesel fuel [22]. 3.4 Spectroscopic Characterization Methods In fresh conditions the catalyst was analyzed by diffuse reflectance infrared Fourier transform (DRIFT-) spectroscopy to determine the NO adsorption state. The DRIFT spectra were measured in the wavelength range of 1500-2300 cm -1 on a Brt~er IFS 88 spectrometer equipped with a Spectra-Tech in situ cell. The spectra resolution was 2 cm -1. The spectra were recorded in situ at 225~ in flowing 2% NO in Helium (50 cm3/min) after preconditioning for 0.5 h at 400~ in hydrogen (50 cm3/min).

4. RESULTS AND DISCUSSION- MODEL GAS REACTOR TEST RESULTS AND SPECTROSCOPIC CHARACTERIZATION DATA

4.1 Influence of Exhaust Gas Temperature Conversion

10C

[%]

75 -0-

CO:

125eC-5000C

HC:

125*C-500*C

NO,: 1 2 5 a C - 5 0 0 ~ C 50

-9e --e-

CO: 500*C HC: 5 0 0 r NOx:500*C

- 125*C - 125~ - 125~

25

0,.-

12s

-~--

-7

2is

,

-~'"

3is

E x h a u s t gas t e m p e r a t u r e

[eC]

425

-

475

-

~ . . . . . . . .

,

Figure 1 CO-, HC- and NO;c-conversion as a function of the exhaust gas temperature. Catalyst: 50 g/fiJ Pt. Model gas test conditions see test 1, Table 2

536 Under realistic diesel engine operation conditions the exhaust gas temperature will switch from low to high temperature and reverse. For this reason NOx-conversion efficiency was tested in the model gas reactor by increasing the exhaust gas temperature from 125~ to 500~ and from 500~ down to 125~ (test 1, Table 2). The NOx-, HC- and CO-conversion efficiency obtained are shown in Figure 1 The results reveal dearly that the catalytic efficiency in this area is independent from temperature decrease or increase.

4.2 Influence of Exhaust Gas HC-Components

75

NO,-CanversJon [%]

......

t 25

0 1GO

75

50

25

0 125

175

225 275 325 375 425 Exhaust gas tomporatt~o (e C]

475 ,u

,-o- Momano ,,,1--- E~ano -,0- Prol:)ano -~.- n-Butane -eo,, n-.Hoptano--:-- Iso..~ctano n..Hoxadocano

Figure 2A: HC- and NOx-conversion as a function of the exhaust gas temperature for different paraffinic hydrocarbons. Catalyst: 50 g/fi3 Pt, fresh. Model gas test condition see test 2, Table 2

537 To evaluate the hafluence of the exhaust gas HC-eomponents the catalyst sample was tested in the flesh condition with various olefinie, paraff'mie, alcoholic and aromatic hydrocarbons. The concentration of the various components was fixed to 3200 ppmC1 (test 2, Table 2). The model gas test results for HC- and NOx-eonversion efficiency are shown in Figure 2A-D The graphs reveal dearly the influence of the C-number per molecule and the nature of the HC-eomponent on catalyst efficiency. Paraffinie hydrocarbons, see Figure 2A, show NOx-eonversion only at higher C-numbers per molecule. Olefinic hydrocarbons, see Figure 2B, reveal NOx-conversion also at low C-numbers per molecule. Alcoholic hydrocarbons, see Figure 2C, show the highest overall activity for NOx-reduction under the applied conditions. Aromatic hydrocarbons Figure 2D show NOx-conversion efficiency depending on the reactivity of the molecule.

75

NO, --Convorsian ('I,1 t

A

5O

25

L

tO0

HC...Convorsl

%1

-i i 5O

2S

0

125

175

225

275

325

375

425

Exhaust gall tomoeraturo [e C|

i ~ (~ylono ~ - - 1-r

~ ~

475

Pfooytlmo 1-OCLINIO

Figure 2B: HC- and NOx-conversion as a function of the exhaust gas temperature for different olefinic hydrocarbons. Catalyst: 50 g/fi3 Pt, fresh. Model gas test condition see test 2, Table 2.

538

N O , - . C o n v ~ , ~ o n [%1 7'5 . . . . .

-

i

Figure 2C:

HC-Con~ion 1O0 :

HC- and NOx-conversion as a function of the exhaust gas temperature for different alcoholic hydrocarbons. Catalyst: 50 g/fi3 Pt, fresh. Model gas test condition see test 2, Table 2.

(%1

75

SO

25

0

125

17S

225 275 :125 375 Exhaust gas tomoorattae (e J,leCnarlo! 1-3~ooanol

75

NO, -.CamM,"~on

~%1 '

t25

475

C!

--,.- [ l/~ano! --'-- 1-.Butanol

i

-

Figure 2D:

100

75

0

HC- and NOx-conversion as a function of the exhaust gas temperature for different aromatic hydrocarbons. Catalyst: 50 g/fi3 Pt, fresh. Model gas test condition see test 2, Table 2

HC--C~mvQrs|on (%1

I

125

175

225 275 325 375 425 Exhaust gas terr~erar,,Ire (e CI

475

: " ' ~ , , Totuene ,-q,,, 1.2..,lylene ~ 2 ~ 1.3-~[ykme i : ~ 1.4-.~[ylono ,,13,- l-.MetnymllDfltl~aline

'i

I

539

In Figure 3 the NOx-conversion efficiency, measured at 225~ is plotted versus the C-number per molecule for all hydrocarbon components tested. As mentioned before, the data clearly reveal that alcoholic and olefinic hydrocarbons exhibit excellent activity for NOx-reduction, but also that n-hexadecane, a component already present in diesel fuel, is a suitable reactant to reach a high NOx-conversion activity level.

NO,-Conversion [%]

7(:

225"C

6(: 5G 4(3 --0-

30 20

L

10 0

5

Paraffins Olefins Alcohols A/ornatl

iso-octane

1'0 C-number/molecule

1'5

17

FigTtre 3: NOx_ conversion as a function of the Cnumber per molecule for different hydrocarbon species. HC-concen-tration 3 2 00ppmC1. Catalyst: 50 g/fi3 Pt, fresh.Model gas test condition, see test 2, Table 2.

4.3 Influence of the Exhaust Gas Hydrocarbon Concentration To evaluate the influence of the exhaust gas hydrocarbon concentration, the Pt based catalyst was tested in fresh condition at a hydrocarbon content of 80012800 ppmC1. Figure 4 shows the NOx-conversion efficiency for exhaust gas temperatures of 225~ 250~ and 300~ (test 3, Table 2). N-hexadecane was chosen as hydrocarbon component. At HC-concentrations above 3200 ppmC] of n-hexadecane the NOx-conversion efficiency is independent of the amount of hydrocarbons introduced. At lower concentration the maximum of NOx conversion was shitted to slightly higher temperatures and decreased. This results show that certain levels of hydrocarbons are necessary to reach acceptable NOxconversion efficiencies. On the other hand the data reveal that high HCconcentrations have no poisoning effect on the catalyst.

540

NO,-Conversion [%] -

70

60 ~

5O 4o

'

-~

,,

z

30

,

20 .

.

O,

"

0

.

i

-.J-C-

=

.

225 ~

250 I C _,-2-- 300 ~

.

.-I'-

2000

~

-

.

10.7.__b_.z_ "

~

,

~

~ i

-~

|

1

i

i

"

'

i

4000 6000 8000 10000 12000 14000 HC-Concentratlon [ p p m C 1]

Figure 4: NOx-conversion for different hydrocarbon concentrations (nhexadecane) as a function of the exhaust gas temperature. Catalyst: 50 g/fi3 Pt, fresh. Model gas test condition see test 3, Table 2. 4.4 Influence of the Exhaust Gas Nitrogen Oxide Concentration

NO,-Conversion [%] , .... 0,..~ _

'

"

0

~

i'

200

~ ~ ~ ~ . ~

!

40O

LI

6O0

-o-0-0-

225 "C 250 ~ 300 eC

'

~

'

NOz-Concentratlon [ p p m |

i ""

8O0

1000

Figure 5: NOxconversion f o r different NO concentrations as a function of the exhaust gas temperature. HC-concentration 3200 ppmC 1. Catalyst: 50 g/fl3pt, fresh. Model gas test condition see test 4, Table 2.

541

The effect of the exhaust gas NO concentration on the NOx-conversion has been studied in the model gas reactor by varying the NO content in the range of 100-80 ppm NO (test 4, Table 2). The hydrocarbon concentration (n-hexadecane) was fixed to 3200 ppmC1. The results obtained are shown in Figure 5. It can be demonstrated that the NO concentration had a significant effect on NOx conversion efficiency at an exhaust gas temperature of 225~ The effect ist negligible at an exhaust gas temperature above 250~

4.5 Spectroscopic Characterization The DRIFT spectrum of Figure 6 shows a peak at 1787 cm-1 at a temperature of 225~ The band is characteristic for a linearly adsorbed NO on platinum [24]. This spectrum gives an indication that the adsorption of NO on Pt sites is a first crucial step for the reduction of nitrogen oxides in the exhaust gas stream.

Adsorl=tion I

225~ 1787 cm "I

o.1

I

23'00 22'00 21'00 20'00 19'00 18'00 17'00 16'00 Wavenumber [ cm'l ]

Figure 6: Diffuse reflectance infrared Fourier transform (DRIFT-) spectrum of the ~latmum based catalyst measured at 225~ in flowing 2% NO m helium (50 cmJ/min)

542 5.

RESULTS

AND DISCUSSION - SELECTIVITY

STUDY AND HYPOTHESIS

OF A

REACTION MECHANISM

The term "space velocity" has established itself as a measure for the exhaust gas flow referred to the catalyst volume. By this definition it is an indication for the residence time of exhaust gas molecules within the catalyst. As mentioned before the inverse residence time plotted versus the selectivity of the reactants gives a tool for the identification of reaction paths. Therefore, the conversion efficiency over the catalyst was measured at 225~ by varying the space velocity (test 5, Table 2). From these data the selectivities S(N2), S(NO2) and S(N20 ) were calculated by using the equations given in chapter 2 and plotted in Figure 7.

100 8O

S NO2, SN20 , SN 2

%

%

%

6O

NO= N=

40 20, 0

s

0

1

2 3 Inverse space velocity

4

Figure 7.: lnitial selectivity for N2, N 2 0 and NO2 as a function of the residence time or inverse space velocity. Catalyst: 50 g/fi3 Pt, fresh. Model gas test conditions see test 5, Table 2. By consideration of the discussed initial selectivity the diagram characteristics and the spectroscopic characterization data can be interpreted in the following way: 9NO2 and N2 are most probably primary products of the reaction 9N20 is most probably a secondary product of the reaction

543 These reported observations can be rationalized by the following sequence of surface (elementary) steps: NO + [S1] ~ NO - [S 1] + 1/2 0 2

NO- [S1] k, ;

(I)

NO 2 - [S 1]

(II)

NO2 + [S1]

(IIA)

k, >

CxHy O2z - [$2]

(III)

NO 2- [S1] + CxHy O2z'[$2]

k, >

1/2N20+xCO2+yH20+[ S1]+[$2] (IVA)

NO - [SI] + CxHy O2z- [$2]

k, >

1/2N2+xCO2+yH20+[ S 1]+[$2]

NO2- [S1] ~ CxHy + zO 2 + [$2]

(IVB)

Figure 8 gives a graphical evaluation of the same sequence.

CxHy + z02 Adsorp~

N2, H20, C02 ~'~ ~Des~176

Interaction/ ~ '

.,>

NO ~Ad$otptJon[.~ *02

.o

Figure 8: Proposed "dual-site" reaction mechanism for NOx-reduction in lean diesel exhaust gas on precious metal containing catalysts Further research and development work it is necessary to proof this hypothesis. Especially the identification of the adsorbed hydrocarbon species is a major task for this work.

544 6.RESULTS AND DISCUSSION- VEHICULE EVALUATION

In preliminary tests the catalyst efficiency was tested on a vehicle dynamometer in the European MVEG-A test cycle. During the first 430 see. of the test cycle no hydrocarbons were added to the exhaust gas stream. In this phase of the cycle the catalyst inlet temperature is in the average lower than 150~ and therefore the exhaust gas temperature does not reach the light-off temperature of the catalyst. After 430 see. till the end (1220 see.) a constant level of 800 ppmC1 of gaseous hydrocarbons was added to the engine exhaust gas stream in front of the catalyst. During this phases of the cycle the exhaust gas temperature is in the range of 200~ to 450~ As hydrocarbon components a butylene/butane (2:1) gas mixture was ehoosen for technical reasons. Figure 9 shows the NOx-, HC- and CO- and particulate conversion rates in the MVEG-A test cycle. The data were obtained after 5011 engine bench aging.

Emissions [%]

100

F3o','.J

80-

[-6o%J 604020O

1

_

CO

HC

,

NO =

!

Particulates

Figure 9: CO-, HC-, NOx- and particulate conversion rates measured in the European MVEG-A test cycle. Catalyst: 50 g/fi3 Pt. Aging 950 h diesel engine bench (see Table 4)

545 7. CONCLUSIONS

It is obvious that a fimher reduction of the tailpipe emission from diesel vehicles by the use of heterogeneous catalysts is a challenging task for both the catalyst and the engine manufacturers. With regard to the catalyst development, the investigations presented in this paper have shown that the first steps are done, but also that additional work is necessary. From this study the following conclusions can be drawn: 9 A reduction of NOx emission in diesel exhaust by injection of hydrocarbons upstream of a catalyst is possible. 9 The model gas experiments have shown that the catalyst activity is influenced by the hydrocarbon concentration, the hydrocarbon component and the Cnumber per molecule of the hydrocarbon used. 9 Alcoholic and olefinic hydrocarbons show the highest overal activity for NOx reduction under these conditions 9 n-Hexadecane, a hydrocarbon component already existing in diesel fuel, shows high an efficiency for NOx-reduction. 9 By a selectivity study and spectroscopic characterization data it was possible to propose a "dual-site" reaction mechanism for NOx-reduction in lean diesel exhaust gas 9 Finally, it was demonstrated in a vehicle dynamometer test according to the European MVEG-A test cycle that it is possible to achieve NOx reduction of approximatelly 30%, combined with CO-, HC- and particulate conversion levels of about 50%, 60% and 45%, respectively. ACKNOWLEDGEMENT

The authors wish to thank all co-workers and colleagues for fruitful discussions. Special thanks to Prof. Dr. H. KnOzinger and N. Schlensog for carrying out the DRIFT measurements and the extremely helpful discussions. Mr. Blumrich, Mr. Fischer and Mr. Emge for the engine vehicle experiments, Mr. Loesche for the model gas experiments, Mrs. Laber, Mrs. Guide and Mrs. Bintz for sample preparation and Mrs. FOrages for carefully typing and preparing the manuscript.

546 REFERENCES

1 R. Beckmann, W. Engeler, E. Mueller, B.H. Engler, J. Leyrer, E.S. Lox and K. Ostgathe: "A New Generation of Diesel Oxidation Catalysts", SAE Technical Paper Series 922330 (1992) P. Zelenka, E.S. Lox and K. Ostgathe: "Reduction of Diesel Exhaust Emissions by Using Oxidation Catalysts", SAE Technical Paper Series 902111 (1990) E.S. Lox, B.H. Engler and E. Koberstein: "Diesel Emission Control", Proc. 2nd Intern. Symp. CAPOC II, Brussels, p. 291 (1990) J. Leyrer, E.S. Lox, K. Ostgathe, B.H. Engler and E. Koberstein: Proc. Intern Seminar "Worldwide Engine Emission Standards and How to Meet Them", IMechE, London, p. 163 (1990) R.W. Horrocks: "Particulate Control Systems for Diesel Engines", IMechE, London, England, Paper C349/87, p. 319 (1987) F. Pischinger, G. Lepperhoff, U. Pfeiffer, K. Egger and G. HOthwohl: "Modular Trap and Regeneration System for Buses, Trucks and Other Applications", SAE Technical Paper Series 900325 (1990) J.R. Needham, D.M. Doyle, S.A. Faulkner and H.D. Freeman: "Technology for 1994", SAE Technical Paper Series 891949 (1989) P. Oser and H. V01ker: "Optimization of Catalyst Systems with Emphasis on Precious Metal Usage", SAE Technical Paper Series 872096 (1987) S. Blumrich and B.H. Engler: "The DESONOX / REDOX-Process for Fuel Gas Cleaning. A Simultaneous Fuel Gas Purification Process for the Simultaneous Removal of NOx and SO2 respectively CO and HC", 1st Conf. Environmental Industrial Catalysis, Louvain-La-Neuve, Belgium, p. 263 (1992) 10 M. Shelef: "On the Mechanism of Nitric Oxide Decomposition over Cu-ZSM-5", Catal. Letters, 15, 305 (1992) 11 G.L. Bauerle, G.R. Service and U. Nobe: "Ind. Eng. Chem. Prod. Res. Develop., 11, 54 (1972) 12 W. Held, A. K0nig, T. Richter and L. Puppe: "Catalytic NOx-Reduction in Non-Oxidizing Atmosphere", SAE Technical Paper Series 900496 (1990) 13 T. Inui, S. Kojo, M. Shibaka, T. Yoshida and S. Iwamoto: "NO Decomposition on Cu-Incorporated A-Zeolites Under the Reaction Conditions of Excess Oxygen with a Small Amount of Hydrocarbons", Zeolite Chemistry and Catalysis, p. 355 (1991) 14 J.O. Petruchi, G. Sill and W.K. Hall: "Studies of the Selective Reduction of Nitric Oxide by Hydrocarbons", Appl. Catal. B:Environmental, 2, 303 (1993)

547 15 C.N. Montreuil and M. Shelef: "Selective Reduction of Nitric Oxide Over Cu-ZSM-5 Zeolite by Water-Soluble Oxygen Containing Organic Compounds", Appl. Catal. B:Environmental, !, L1-L8 (1992) 16 M. Iwamoto and H. Hamada: "Removal of Nitrogen Monoxide from Exhaust Gases Through Novel Catalytic Processes", Catal. Today, 10, 57 (1991) 17 M. Iwamoto, N. Mizuno and H. Yahiro: "Selective Reduction of NO and Hydrocarbon in Oxidizing Atmosphere", Proc. 1st Joint Workshop of Catalytic Science and Technology (JECAT), Tokyo, Japan, p. 199 (1991) 18 H. Hamada, Y. Kintaichi, T. Yoshinari, M. Tabea, M. Sasaki and T. Ito: "Performance of Solid Acid Type Catalyst for the Selective Reduction of Nitrogen Oxides by Hydrocarbons and Alcohols, 1st Conf. Environmental Industrial Catalysis, Louvain-La-Neuve, Belgium, p. 219 (1992) 19 B.H. Engler, J. Leyrer, E.S. Lox and K. Ostgathe: "Catalytic Reduction of NOx with Hydrocarbons Under Lean Diesel Exhaust Gas Conditions", SAE Technical Paper Series 930735 (1993) 20 Z. Chajar, M. Primet, H. Praliaud, M. Chevrier, C. Gauthier, F. Mathis and E.S. Lox: "Influence of the Copper Dispersion on the Selective Reduction of Nitric Oxide over Cu/A120 3 Catalysts: Nature of the Active Sites", Proc. 3rd Intern. Symp. CAPOC III, Brussels (1994) 21 O.H. Hougen and K.W. Watson: "Chemical Process Principles", J. Wiley, New York (1947) 22 G.F.Froment and K.B. Bishoff: "Chemical Reactor Analysis and Design", J. Wiley, New York (1979) 23 German Specifications of Automotive Diesel Fuel, DIN 51601 (1986) 24 B.A. Morrow, J.P. Chevrier and I.E. Moran: "An Infrared Study of the Adsorption of NO on Silica-Supported Platinum over a Wide Temperature Range", J. Catal., 91,208 (1985)




549

CATALYTIC OXIDATION OF DIESEL SOOT: CATALYST DEVELOPMENT

John P.A. Neefi, Olaf P. van Pruissen, Michiel M a k k e e and Jacob A. Moulijn*

Delft University of Technology, Section Industrial Catalysis P.O. Box 5045, 2600 GA Delft, The Netherlands ABSTRACT A number of metal oxides was screened upon catalytic activity for soot oxidation by means of TGA/DSC. Several metal oxides appeared to be active soot oxidation catalysts. Contact between catalyst and soot was found to play a major role in this solid-solid-gas reaction; varying this contact, activities for several catalysts ranged from active to hardly any activity. It is further tentatively suggested that contact of soot, deposited on catalytic coated particulate filters, is poor, which has major implications for the development of soot oxidation catalysts under diesel operation conditions.

1 INTRODUCTION

After the successfid hltroduction of the three way catalyst for otto engflaes ha the 80's, attention has been focused on the emission characteristics of diesel engines during flae last decades. It was fotmd that NO• and soot (better: particulates) are the main contributors from diesel engflaes to environmental pollution and health hazards. Therefore, NO• mad particulate standards have tightened, and will tighten in years to come, which resulted ha the latmclmag of large research projects worldwide. At Delft University of Teclmology, in 1990 the project 'Catalytic removal of soot and NOx from diesel exhaust gases' was haitiated. Within the soot part of the project, the attention is being focused on the development of a catalytic soot filter as an add-

The authors would like to acknowledge financial support for the DUT-project 'Catalytic removal of soot and Noxfrom diesel exhaust gases' by the Dutch Ministry of Housing and the Environment (VROM).

550 on device for diesel engines, as well as on the chemical processes taking place at a smaller scale when soot is combusted over a catalyst. Catalytic oxidation reactions of carbonaceous materials have been extensively studied. Carbons, chars, and graphites have been oxidized catalytically under carefially controlled steady state conditions in order to accurately determine reaction rates. Often, high purity carbonaceous materials were used in combination with low catalyst and oxygen concentrations. In others studies, ignition of carbonaceous materials was studied under less well controlled conditions. The reaction rate of catalyzed carbon oxidation reactions depends on a number of hatrinsic parameters: 9 The carbonaceous material used. Its reactivity depends on the hydrogen-to-carbon ratio, the surface area, the ash content, and the amotmt of adsorbed components, in particular hydrocarbons. 9 The catalyst used, including its preparation. 9 The catalyst-to-carbon ratio. 9 The contact between carbon and catalyst, as will be discussed shortly. 9 Pretreatlnent of the sample. For example, the amotmt of adsorbed hydrocarbons on soot is known to decrease as a fimction of thne; an initial heat-up ha inert gases leads to desorption of hydrocarbons and it may have other effects, as a change in contact between soot and catalyst, or a reaction between soot and metal oxide, reducing the catalyst. 9 Oxygen partial pressure. The soot oxidation rate was found to depend linearly on the oxygen partial pressure [1,2]. The reaction rate can be measured in various ways. In this study, Thennogravimetrical Analysis (TGA) ha combhlation with Differemial Scamling Calometry (DSC) was used. Also this teclmique mad the experilnental method can iaffluence the observed reaction rate. The following parmneters are of hnportance: 9 The sample mass, the gas flow rate, and the specific geometry of the thennobalance. These parameters hffluence heat and mass transport to and from the sample and determine when, at high carbon oxidation rates, heat production will pass a threshold value after which the carbon will ignite. 9 The telnperature history of the sample. Peak telnperatures (temperatures at highest mass loss rate) shift to lower temperatures as heating rates decrease. In literature, not always sufficient attention is paid to these parameters. In catalytic carbon and graphite studies, as reviewed by McKee [3], experimental conditions are usually thoroughly controlled and described. In soot oxidation studies for diesel aflertreatlnent purposes (e.g. [1,4-7]), experilnental conditions are often less carefidly reported. As also the intrfiasic parameters in these two types of studies differ (low oxygen and catalyst concentrations ha the former type of experhnents versus high

551 concentrations ha flae latter; often very small, nanometer-scale catalyst particles in the former experiments versus large, micron-scale particles in the latter), results from one type of study cannot be used in the other type of study without due consideration. The objective of this study is to investigate the influence of above mentioned intrinsic parameters of catalyst and soot on the catalytic combustion of soot. In order to be able to study these parameters, first the activity of different soot oxidation catalysts has to be defined properly. The screenhag of catalyst materials, as presented in this paper, aims to fiflfil this need. A second objective of tiffs paper is to assess file ilffluence of-according to our views- one of the most ilnportant parameters apart from the type of catalyst used; flae contact between soot and catalyst. So far, little attention has been paid to this parameter in soot oxidation literature. 2 EXPERIMENTAL

As file composition of diesel particulates (e.g. fraction of adsorbed hydrocarbons) depends upon many motor characteristics as engine load, speed, and various temperatures, it is difficult to collect batches of soot with constant properties. Therefore, we choose to work with prhatex-U (a flame soot supplied by Degussa AG) as a model soot. Properties of this model soot and diesel particulates collected from a one cylinder direct hljected diesel enghle (Yananar L90E diesel generator set) are listed ha Table 1.

Table 1: Some properti, 's of Printex-U (model soot) and diesel particulates Elementary analysis (wt%) C H

Printex-U

Diesel particulates

92.2 0.6

90.1 2.4 55+ 10 (at 0% load) 24+8 (at 75% load) 10+5 (at 100% load)

wt% volatiles* Surface area (BET)

100 m2/g

60 - 85 m2/g

Elementary particle size

25 + 3 lull

20+3 run (at 75% load)

*: desorption as measured by TGA weight loss in N2 to 960 K.

552 Ial the catalyst screenfilg experfinents, powder-form catalysts were used, which were milled and sieved. The fractioo smaller than 125 mm was used. Activities of soot oxidation catalysts were determined using an STA 1500H thennobalance (combined TGA and DSC). A heating rate of 10 K/min and a flow rate of 50 ml/min 21 3.0 vol% 02 in N2 were used. Thermal ~* 2.0 ~N rtmaways were observed when usfiag too large soot samples or ~ 1.0 samples that were not diluted, as is demonstrated in Figure 1. These "~o.o o thermal runaways ('ignitions') cotdd .:--., :Di!.u~..ed.samplcl(2 nag soot) .....i.;~ be avoided using small, diluted 400 ~" samples. Silicon carbide (SIC) was 300 _= fotmd to be a proper, h~ert material 'D,.~'~' 200 '-_ havfiag a lfigh heat capacity as well 100 as a high thermal conductivity. Employfiag sample sizes of 2 mg 0 soot and 4 mg catalyst, diluted with about 55 mg SiC, thennal runaways as well as strong heat-up of the samples dumlg soot oxidation were Temperature (K) avoided and smooth and Example of thermal runaway reproducible combustion peaks Figure 1 were observed. The maximum of (sharp peak in upper DSC curve). A simultaneous sharp temperature increase these peaks named combustion is observed (discontinuation in temperature (Tcomb), determined by TGA-curve) the heat flux (DSC) signal (which coincides wiflain 10 Kelvin wifla flae peak of the slightly noisy derivative mass signal), was used as a first indication for catalyst activity. Combustion temperatures could be reproduced within typically 5 K for flae same catalyst batch. 111 order to ilwestigate the influence of contact between soot and catalyst on soot combustion temperature, two methods were employed to prepare soot catalyst mixtures: firstly milling a mixture of fl~e soot and catalysts, using a mechanical agate mill; tiffs type of contact is referred to as tight contact, and, secondly, just physical contact by shakfi~g soot and catalyst fil a sample bottle, which will be referred to as loose contact, ha all experiments a catalyst-to-soot ratio of 2 (on weight basis) was used.

!

553 For evaluation purposes, particulates from a one cylinder diesel engine were collected on catalyst powder as well as on small segments of catalyst impregnated wall flow monolith (EX-47 from Coming) to be able to assess the degree of contact when collecthag soot on filters coated with a catalyst. These segments (diameter of 12.5 mm and lengfll of 20 nun) were impregnated with Co(NO3)2- or Cu(NO3)2solutions, or washcoated with 3,-A1203 particles which had in a previous step been coated with cobalt by wet impregnation of Co(NO3)2. The segments were calcined at 675 K, then the alternate channels were closed using an alumina sol based glue, and subsequently the segments were dried and calcined at 1000 K. 3 RESULTS AND DISCUSSION Screening of catalysts During the catalyst screening tests, it became readily clear that contact between soot and catalyst played a very ilnportmat role h~ the catalytic oxidation of soot. Among the catalysts showing activity ha tight contact with soot, some catalysts showed also activity in loose contact. Others, however, did hardly or did not. Two examples are shown in Figtu'e 1 (Co304) and Figure 3 (MOO3). The activity for MoO3 in loose contact mode is still considerable, wlfile Co304 has hardly any activity in loose contact mode. As it is not clear which contact is important in soot oxidation in diesel applications, both combustion temperatures were measured for a series of catalysts showing activity in tight contact mode. Results are summarized in Figure 1. For a ntunber of catalysts, two different oxides have been tested. For lead, no significant difference was fotmd h~ combustion temperature starthag from either oxides PbO and PbO:. For copper, a higher combustion temperature was fotmd for cuprous oxide (T~omb,c , o - 797 K) thin1 for cupric oxide (T~omb,c,o = 763 K). Silver oxide (Ag20) decomposes between 490 and 530 K, so that the actual catalyst was probably metallic Ag. For Co304, quite a large range of combustion temperatures was fotmd ushlg different batches of Co304: from 664 to 762 K. The largest ntunber of data was fotmd close to 685 K. The exact reason for this lack of reproducibility is not yet tmderstood. For Cr203, hfitially lower combustion temperatures were found as those presented ha Figure 1. Small alnotmts of CrO3, which was used as the precursor salt for Cr203, were thought to cause tlfis irreproducibility. CrO3 is more active than Cr203, but it decomposes to Cr203 upon reaction with soot.

554 2.0

2.0 (M}

~10

~,

- 1.0 9

o'1 o'J

2-0.0

E0.0 ...

O O

.

.

.

.

.

.

.

.----.Co~O,lsoot. in d~ht contact -............... . , - .. ........:~:co~o JSoot iix.-Itrust:-contact: :::i:" -::-.Soot.(no catalyst):Blank ..:

.

..,

.

..

O O

---.-- MoOrish:rot m I.ocrsc contact Soot (no catalyst): Blank

ou

.

,,,

9

.

I00 E

ilf~N

50 ~ I

,

500

i

,

600

1

700

i

I

800

,

0

I

500

900

Figure 2 Tight and loose contact mode soot oxidation: Co304

T combustion (K)

600

,=.

I150=~ rm

I00

I

!

|

700

800

900

Figure 3 Tight and loose contact mode soot oxidation: MoOs

m" Tight contact

~ " Loose contact

[~l" Blank

900 ~

800

700

600 I

I

Blank oeo.I w'o31 ' SnO:

Nb._O~ C e O :

BaO

Cr:O3

Ag~O

CaO

.

Sb:Os La,.O~ M o O 3

PbO

Co30,

Figure4 Model soot combustion temperatures in tight and loose contact mode

-~

555 A classification of the catalysts screened is shown in Table 2.

Table 2: Classification of catalysts according to tight and loose contact mode activity. Tight contact: Hardly or no activity (Tcomb> 800 K): GeO2, SnO2, WO3, NbzO5, MgO, CeO2, ZnO, BaO, Zr02

Moderate activity (800 K > Tcomb> 700 K)

High activity (Tcomb< 700 K)

Cr203, NiO, Ag20, CuO, CaO, Bi203, SbaOs, MnO2, La203, FezO3, MOO3, V205

Co304, PbO

Loose contact Hardly or no activity (Tcomb> 850 K): NiO, CaO, Bi203, MnO2, La203, Fe203, V205, Co304

Moderate activity (850 K > Tcomb> 700 K): Cr203, CuO, Ag20, PbO, M003, 8b205

As cma be seen ha Table 2, only Cr203, CLIO, Ag:O, PbO, MO03, mad Sb205 show high or moderate activity in tight as well as in loose contact mode. The oilier catalysts fotmd to be active ha tight contact mode, showed no activity ha loose comact mode. Oxidizfilg graplfite using low catalyst concentrations, Amariglio and Duval [8], Heintz and Parker [9], and Magne and Duval [10] fotmd high activities for the oxides of Pb, Mn, Ag, Cu, V, Au, Ba, Cd, m~d Ni. McKee [11], detennilfing ignition telnperatures of graphite-catalyst lnixtures, found several metal or metal oxide catalyst to be active (in order of decreasing activity): Pb, V, Mn, Co, Cr, Cu, Mo, Ag, Cd, Fe, Pt, Ni, Rh, Ir, Ru, Pd, Ce, Zn, W, Hg, mid Sn. McKee fitrther reported the trioxides of As, Sb, and Bi to be moderately active catalysts [3]. These data are more or less consistent with our ranking of catalysts; ahnost all the active and moderately active catalyst ha tight contact mode, as shown in Table 2, are also reported active ha above mentioned studies [3,8-11 ]. Alkali compotmds are known to be active carbon oxidation catalysts (as reviewed ha [3]). Results for Li, K, Na, mad Cs are not reported here as problems were encotmtered, preparing soot-alkali hydroxide mixtures, followfilg our tight and loose contact mode procedure.

556 Precious metals were not examined in this study. These metals are too expensive to be used in large amounts in particulate filters. Using low amounts of catalyst, as in flow-through oxidation catalysts, we expect the contact between precious metal and soot to become a problem. Besides, sulfur dioxide oxidation over precious metal catalysts cml form a large problem under practical conditions [12]. Contact between soot and catalyst The difference between soot oxidation in loose and tight contact with catalyst is remarkable for some catalysts; using C0304, V205, Fe203, La203, MnO2, and NiO, high or moderate activities are found in tight contact mode while in loose contact with soot hardly any activity is fotmd. Other catalysts; PbO, MO03, Sb205, CuO, Ag20, and Cr203, exhibit also activity hi loose contact mode, although this activity is lower than the activity hi tight contact mode (see Figure 1). ha literature, the activity of graphite oxidation catalysts has been correlated to the mobility of the catalyst, as expressed by the Tamman temperature of the metal or metal oxide, being the temperature at which the lattice atoms of the compound become mobile. This Tanunan temperature was found to be roughly half the melting temperature (Tin) hi Kelvfla [13]. Besides, some metal oxides exert a measurable vapour pressure in the temperature whldow of this study, e.g. MoO3 and Sb205 [14]. This mobility does not provide an explanation for our data: It would explafll the high loose contact mode activities of PbO (Tm = 1159 K), MoO3 (decomposes, MoOz: Tm = 1068 K), Sb205 (decomposes via Sb204 to Sb203 with Tm = 929 K), possibly CuO (Tin = 1599 K, Cu: Tm = 1356 K) and Ag20 (decomposes, Ag: Tm = 1235 K), but it fails on vmladitun and bismuth, also having low melthlg temperatures (V205: Tm = 963 K, Bi203: Tm = 1098 or 1133; phase-depending) and on chromium, which is moderately active ha loose contact mode although it has a high melting pohat (Cr203: Tm= 2266 K) [15]. h~ screenh~g bulk solids it appears that the smnple lfistory is quite hnportmat [16], e.g. co~ranercial PbO samples contahl a large mnount of carbonates, Milch decompose upon heating at high temperature. The observation of low activities for active catalysts, when the soot-catalyst contact is poor, lnight have ilnportant implications for catalysts used ha diesel exhaust applications, h~ order to assess the contact between soot collected on a filter coated wifla a catalyst, two other expel-hnents were performed, ha the first experiment, diesel particulates were collected on large 250 lrnn Gehnan Sciences Type A/E filters, of Milch a well defined part was covered with catalyst powder. Subsequently, the soot was combusted in a thennobalance usfi~g stm~dard conditions as flow rate m~d heating rate. Results for a Co304 catalyst are showal in Figure 3. In tlfis figure, the combustion temperatures are fi~dicated in the DSC patterns by their telnperatures: 668, 765, and 881 Kelvin for tight contact with hydrocarbon-desorbed soot, tight contact, and collection on catalyst powder, respectively. Furtherlnore, in the DSC patterns two

557 sharp soot ignitions are visible fil the tight contact curve for both the straight contact as well as the tight contact after desorption of hydrocarbons. In the tight contact mode curve also two small hydrocarbon combustion peaks can be seen. From tiffs figure it becomes clear that diesel soot, collected on catalyst powder, combusts at a temperature comparable to loose contact mode combustion of Prfiltex-U and Co304 (see Figure 1). The same soot, collected on a filter without catalyst, shows a higher activity when milled with a C0304 catalyst. Tiffs activity, however, is lower than the tight contact mode activity m Figure 1. Probably the adsorbed hydrocarbons cause 6.0 ~'"' 5.O ."

,~4.0 ~3.0 ~2.0 ~0.0

500

66s

250

400 500 600 700 800 900 Temperature (K)

Figure 5 Influence of contact on Co~04 catalyzed soot oxidation. Diesel soot (75% load) is used. tlfis effect; when these hydrocarbons are desorbed fil fiaert atmosphere before the diesel soot is milled with the Co304 catalyst, an activity was found sfinilar to the tight contact mode combustion with model soot shown fi~ Figure 1. In a second experhnent, segments of wall flow monolith hnpregnated with Co304 or CuO, were placed in a holder in the diesel exhaust gas, and diesel exhaust gas was sucked through the monolith by means of a gas pump. In tlfis way, particulates were deposited on the segmems of wall flow monolith. The soot was succeedhlgly burned hi a thennobalance. The restdts of these tests were that, using C0304 or CuO catalysts, no large catalytic activities could be fotmd: although soot combustion started at about 100 K lower thin1 was observed for blmak wall flow monoliths

558 without a catalytic coating (about 700 K versus 800 K), the catalyst impregnated segments of monolith showed a similar soot combustion temperature as the segments of monolith without a catalyst. From these tests it seems that, using catalysts being not or moderately active in loose contact mode (see Table 2), catalytic coathlgs on a particulate filter are not able to catalyze soot oxidation. The contact between soot mad catalyst is probably poor under these circumstances and resembles the loose contact. This contact is apparently too poor to significantly enhance the soot oxidation rates. Our observation was made for a wall flow monolith, which is a surface filter (particulates are deposited on top of the filter surface). The contact between soot and filter surface and between soot and catalyst is not expected to be better in other particulate filters. In all these filters, including ha filters acting on a deep filtration mechanism (particulates are deposited throughout the filter structure), the driving force for particulate collection is ditfiasion. Density of soot particulates is too low to enable an hnpaction mechm~ism to play a role in particulate filtration. In literature, some supports for this poor contact between soot and catalyst are given. Precious metals are reported to give only a minor decrease of soot ignition temperatures [5,17]. Base metals showed a higher activity (up to 150 K [5,18]), which is, however, low compared to the up to 300 K reduction in ignition temperature observed ushag fuel additives [19,20]. L6we and Mendoza-Frolm [21] exmnfiled a model soot shnilar to the soot used hi this study mad brought it hi contact with a Pt/Co/La catalyst in a nmnber of ways. They come to the same observations as reported fi~ fltis paper when they compared soot, ilnpregnated with catalyst, with soot, pressed or sprfiMed upon catalytic layers. Their best results were obtahaed when the soot was hnpregnated with a catalyst solution. They argue that contact, h~stead of the amount of catalyst, causes higher soot oxidation rates. Moreover, our experhnents show that, when usfiag hatrfi~sically active catalysts (catalysts active in tight contact mode), the degree of incapability of enhancfilg soot oxidation rates is dependent on the properties of the catalyst itself. Some catalysts cm~ significantly increase soot oxidation rates when contact between catalyst mad soot is poor, whereas for other catalysts no hacrease was observed. Currently we are fitrther investigathag the contact between soot mad catalyst, hmluding possibilities for optimization of this contact. A ntunber of methods to establish a better contact seems to be feasible, ha literature, some groups have reported on the use of small inorganic fibres or whiskers in order to 'blow up' the washcoat and catalyst, within typical diesel particulate dhnensions (typically 0.2 - 1 Nn). Although very low soot ignition temperatures were published (Saito [22]), we have not been able to duplicate these results. A second possibility to ameliorate contact is 'brfi~ghlg the soot to the catalyst'; some kind of mechmtical means to establish tighter contact. For a nmnber of reasons (lfinited strength of filters,

559 tmfavourable mechanical constructions in diesel exhaust gases) fllis option seems to be irrelevant. A third and more feasible option seems to be %tinging file catalyst to the soot', wluch we already discussed explahtfllg the loose contact mode activities. Additional experiments indicate that other, modified catalyst formulations are very active soot oxidation catalysts, which is caused by their improved mobility. However, tlus mobility has a drawback: Deactivation rates of the catalyst are highly increased and catalyst deactivation becomes a very important catalyst design parameter. It may be clear that these types of catalysts are still in an explorative state. We know of no literature data, reporting on studies trying to improve catalyst mobility. Our data will be published ha another paper. Fourth and finally, an extensively studied option is file use of organometallic fuel additives, fll wluch an ilnproved contact between soot and catalyst seems likely. Upon combustion, the organometallic species are decomposed, resulting in metal oxide or sulfate particles dispersed ha the soot particulates. Only a few data has been collected upon dispersion of the catalyst and the contact between catalyst and soot (Otto and coworkers showed a good dispersion of a lead catalyst in soot particulates [23]). From ignition temperature measurements and field tests using wall flow monoliths in combhaation with filel additives, it seems that the activity of these catalysts (including catalysts not active in loose contact as cerium oxide and manganese oxide [24,25]) is quite high. This indicates that the comact between soot and catalyst is better than loose contact.

CONCLUSIONS

A large ntunber of metal oxides shows activity for the soot oxidation reaction, in case of good contact between soot and catalyst. The most active catalyst fotmd fll tllis study are, fla order of decreasing activity, PbO, C0304, V205, MOO3, Fe203, La203, MnO2, Sb205, Bi203, CuO, Ag20, NiO, and Cr203. A ntnnber of ways was employed to make contact between soot aa~d catalyst. It was shown that the contact between soot and catalyst is of prime importance for the reactivity of the catalyzed soot oxidation. Several catalysts were fotmd to be unable enhancing the soot oxidation rate when the contact between soot and catalyst is poor. This explaflls why catalyst coated particulate filters have been found quite inactive under practical conditions. For catalytic systems which seem to be able to decrease soot combustion temperatures a possible explanation can be probably fotmd in catalyst mobility. As lnethods, brflagfllg soot and catalyst hato contact, greatly differ (or are not even memioned) ha different studies, the activities of catalysts as described hi carbon, soot or graphite oxidation studies may Olfly be compared qualitatively.

560 REFERENCES

1

10 11 12 13 14 15

Ciambelli, P.; Parrella, P. and Vaccaro, S., Kinetics of soot oxidation on potassium-copper-vanadium catalyst, In: Catalysis and Automotive Pollution Control II, (Ed: Crucq, A.) Elsevier Science Publishers, Amsterdam, 323-35 (1991). Lin, C. and Friedlander, S.K., Soot oxidation in fibrous filters. 2. Effects of temperature, oxygen partial pressure, and sodium additives, Lallgmuir 4(4), 898-903 (1988). McKee, D.W., The catalyzed gasification reactions of carbon, In: Chemistry and physics of carbon, Vol. 16, (Eds: Walker, P.L.J. and Thrower, P.A.) Marcel Dekker, New York, 1-118 (1981). Ahlstr6m, A.F. and Odenbrand, C.U.I., Catalytic combustion of soot deposits from diesel engines, Appl. Catal. 60(1), 143-56 (1990). Niura, Y.; Ohkubo, K. and Yagi, K., Study on catalytic regeneration of ceramic diesel particulate filter, SAE Paper 860290 (1986). Hillenbrand, L.J. and Trayser, D.A., A concept for catalyzed ignition of diesel soot, SAE Paper 811236 (1981). Watabe, Y.; Irako, K.; Miyajima, T.; Yoshimoto, T. and Murakami, Y., "Trapless Trap"- A catalytic combustion system of diesel particulates using ceramic foam, SAE Paper 830082 (1983). Amariglio, H. and Duval, X., Etude de la combustion catalytique du graphite, Carbon 4, 323-32 (1966). Heintz, E.A. and Parker, W.E., Catalytic effect of major impurities on graphite oxidation, Carbon 4,473-82 (1966). Magne, P. and Duval, X., Comparaison des effets catalytiques de divers m6taux dans les r6actions graphite-oxyg6ne et graphite-protoxyde d'azote, Bull.Soc.Chim.France A5, 1593-7 (1971). McKee, D.W., Metal oxides as catalysts for the oxidation of graphite, Carbon 8(5), 623-35 (1970). Ball, D.J. and Stack, R.G., Catalysts for diesel powered vehicles, In: Catalysis and Automotive Pollution Control II, (Ed: Crucq, A.) Elsevier Science Publishers, Alnsterdam, 337-51 (1991). Baker, R.T.K., In situ electron microscopy studies of catalyst particle behavior, Catal.Rev.-Sci.Eng. 19(2), 161-209 (1979). Knacke, O.; Kubaschewski, O. and Hessehnalm, K., Thermochemical properties of inorganic substances, Vol. I and II., Springer-Verlag, Berlin, 2412 pages (1991). Weast, R.C. mad Astle, M.J., Handbook of chemistry and physics, 62nd ed., CRC Press, Inc., Boca Raton (Florida) (1981).

561 16 Amoldy, P.; Heijkmlt, J.A.M.van den; Bok, G.D.de and Moulijn, J.A., Temperature-programmed sulfiding of MoO3/A1203 catalysts, J. Catal. 92, 35-55 (1985). 17 Koberstein, E.; Pletka, H.-D. mad V61ker, H., Catalytically activated diesel exhaust filters - engine test methods mid results, SAE Paper 830081 (1983). 18 Pattas, K.N.; Stamatellos, A.M.; Patsatzis, N.A.; Kikidis, P.S.; Aidarinis, J.K. and Samaras, Z.C., Forced regeneration by exhaust gas throttling of the ceramic diesel particulate trap, SAE Paper 860293 (1986). 19 Daly, D.T.; McKinnon, D.L.; Martin, J.R. and Pavlich, D.A., A diesel particulate regeneration system using a copper fuel additive, SAE Paper 930131 (1993). 20 Rao, V.D.; White, J.E.; Wade, W.R.; Aimone, M.G. and Cikanek, H.A., Advanced teclmiques for thermal and catalytic diesel particulate trap regeneration, SAE Paper 850014 (1985). 21 L6we, A. and Mendoza-Frolm, C., Zum Problem der Dieselrub-Verbrennung auf einem katalysatorbeschichteten Filter - der Kontakt zwischen Katalysator und Feststoff, Chem.-Ing.-Tech. 62(9), 759-62 (1990). 22 Saito, K.; Ueda, K. and Ikeda, Y., Exhaust gas cleaning catalyst and process for production thereof, European patent application 0211233, Filed 1-7-86, Issued 25-10-89. 23 Otto, K.; Lelunan, C.; Bartosiewicz, L. and Shelef, M., Carbon oxidation catalyzed by lead, Carbon 20(3), 243-51 (1982). 24 Pattas, K.N. and Michalopoulou, C.C., Catalytic activity in the regeneration of the ceramic diesel particulate trap, SAE Paper 920362 (1992). 25 Wiedemalm, B.; Doerges, U.; Engeler, W. and Poettner, B., Application of particulate traps and fuel additives for reduction of exhaust emissions, SAE Paper 840078 (1984).




563

CATALYTIC COMBUSTION OF DIESEL SOOT ON PEROVSKITE TYPE OXIDES W. Sri Rahayu, L. Monceaux, B. Taouk and P. Courtine Ddpartement de Gdnie Chimique, Universitd de Technologic de CompiOgne, B.P. 649, 60206 CompiOgne C~dex, France

ABSTRACT The combustion of soot particulates is studied on perovskite type oxide catalysts having the general formula : La0.8Sr0.2Mnl.x_yB'x~yO 3 ( B ' = Pt, Ru or Pd, x < 0.01, and F represents a deficiency in B site, y < 0.09). In order to determine the relative activity of various catalytic compositions, TGA and DTA experiments are performed on a mixture of catalyst and soot under air flow. The ignition temperature (Ti), the temperature of the maximum of combustion rate (Tin) and the soot conversion are determined. Soot is simulated either by a mixture of carbon black, fuel and lube oil or by carbon black alone. After a screening, the best catalytic results are obtained for two compositions, i.e. Lao.sSro.2Mno.999Pdo.0010 3 and Lao.sSro.2Mno.91~0.090 3. In both cases, the combustion temperature (Tin) of carbon black is found to be lowered from 650~ to about 440~ The influence of several parameters on the catalytic properties of these latter formulations is studied : catalyst preparation method, specific area, ageing, carbon black/catalyst ratio.

1.INTRODUCTION

Compared to gasoline engines, diesel powered automobiles emissions are low in carbon monoxide but, unfortunately, they contain a higher proportion of NOx and soot particulates which have a serious impact on urban air quality and human health. Therefore, legislation makes it a duty to siglfificantly reduce these emissions [1]. Soot particulates may be separated from the exhaust stream by filtration through a porous trap [2], but this device causes the increase of exhaust back pressure and therefore affects fuel economy and vehicle performance, consequently traps must be periodically regenerated by oxidizing the collected particulates. Several methods are used in order to regenerate traps. These

564

methods can be divided into catalytic and non-catalytic ones. In the first case, fuel additives [3, 4] and catalytic trap coatings are necessary [5-13] whereas in the non-catalytic case, the trap is electrically heated or with the help of a burner. As fuel additives may cause engine disorders and extemal heating may lead to the trap destruction, then, it seems that catalytic trap coatings could be a satisfying alternative. Different kinds of catalysts have already been studied. Research works in this field proceeded through noble metals and transition metals or alkaline oxides based catalysts. Pt and Pd, though showing some activity [5-7], cause serious problems, as they are poisoned by sulphur. It has been shown that catalytic performance and durability are improved by using noble metals doped praseodymium, neodymium and samariuln oxides [ 13]. Comparison between oxides of copper, manganese, chromium and vanadium shows that V205 is one of the most active catalysts for the combustion of diesel soot [10]. Catalyst made up of V205 and CuO with a molar fraction 0.9 in vanadium leads to an elflmncement of the activity [11]. Another screening study on oxides of potassium, vanadiuln, copper, manganese and cobalt shows that the systems (K-V-O) and (K-Cu-O) can reduce the ignition temperature of carbon black of about 260~ [12]. It is to be noticed that no study about the stability of these compounds is reported. Then, the purpose of this study was to investigate the possibility of lowering of combustion temperature of diesel soot particulates by using perovskite type oxides (ABO3) as catalysts. These phases are known to be good catalysts for total oxidation of hydrocarbons and CO. They are thermally and chemically resistant. It is possible to introduce in their structure little amount of noble metals or other ions [14, 15]. The basic formula of the studied phases is Lao.2Sr0.sMnO3 doped or not by platinum, palladium and n~thenium. To evaluate the catalytic activity of catalysts, thennogravimetric (TGA) and differential thermal analysis (DTA) are used. 2. EXPERIMENTAL PROCEDURE

2.1. Preparation of perovskite catalysts The studied catalysts have the following general formula : Lao.aSr0.8Mnl_x_yB'x~)yO3_x where B' is a noble metal (Pt, Pd and Ru), F cation vacancies and 1 refers to the oxygen non stoichiometry. The perovskite phases are obtained by decomposition of equimolar mixtures of the corresponding metal nitrates (La, Sr and Mn) and noble metal (Pt, Pd mad Ru) chlorides.

565 The precursors are synthesized by a sol-gel process. This method that was developed and accorded to Baythoun et al. [16], consists in dissolving, gelating, drying and activation steps. The salts are dissolved, in either water (hereafter first method), or ethylene glycol as solvent (second method) with citric acid. i) In the first case, a solution of mixed salts is evaporated to dryness at 80~ and the gel obtained is dehydrated at 60-70~ for 5 hours and calcined with a heating rate of 5~ for 6 hours at 600~ under air. ii) In the second case, the mixtures are stirred while heating around 80-110~ tmtil the sol is obtained. The as-prepared gels are dried and calcined by heating rate of 5~ under air, for 6 hours up to 600~ for crystallization.

2.2. Preparation of simulated diesel soot The simulated diesel soot is synthesized by a mechanically mixing of carbon black (70%), diesel fuel (15%) and lube oil (15%). The carbon black used (Regal 660 supplied by the Cabot France Co) has a specific area of 112 m2/gr., and the particle size is around 0.24 lam in diameter. 2.3. Activity test The combustion of diesel soot is conducted using TG-DTA Setaram 92. Sample to be analyzed is prepared by mixing catalysts with simulated diesel soot or carbon black alone and grinding in an agate mortar. Then it is loaded in a platinum crucible on initial weight around 66 mg. The experimental conditions are 6~ of heating rate from 20~ to 600~ 1.5 1/h of oxidizing atmosphere flow. The computer system allows to draw both TGA and DTA curves as shown in Figure 1. TGA curve gives the conversion of diesel soot mad the ignition temperature Ti. On the other hand, DTA curve provides the maximal rate of oxidation corresponding to the top of the exothermic signal (Tm). 2.4. Characterization of samples The specific areas of samples are measured using a triple point BET method of the nitrogen adsorption at 77K on a Quantasorb Jr. surface area analyser. The X-ray diffraction (XRD) analysis of the samples is carried out with an Xray powder diffractometer using CuKa radiation and curved sensitive detector. Temperature-progratmned desorption (TPD) is carried om under vacuum (~10-6mbar). Prior to each run the sample is treated in air stream at 600~ and then cooled to room temperature. Then, the temperature of the sample is raised at a constant rate of 10~ under vacuum. Oxygen, CO and COa are detected using a quadrupole mass spectrometer (QTMD Carlo Erba).

566

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Figure 1. Thermal analysis (TG and DTA) of" a) simulated soot " b) mixture of LMPds catalyst and soot (15 wt %)

3. RESULTS 3.1. Catalytic Test Reactivity of simulated soot 9Results obtained with the simulated soot without catalyst are shown in Figure 1.a. Two steps of weight loss are observed. In the temperature range 150~ to 400~ a 25 % weight loss is assigned to oxidation of hydrocarbons (filel and oil). hi the range 500~176 a second loss corresponds to the oxidation of carbon black. The DTA curve shows two exothermie peaks at 350~ and 670~ associated respectively with hydrocarbons and carbon black oxidation. With dry carbon black, no modification on ignition temperature of the particulates is observed.

567 Screening : TG and DTA experiments are carried out with mixtures of soot and catalysts.~Jn Table 1, ignition temperature T i and maximum rate of combustion Tm are noted and related to temperatures obtained for soot combustion without catalyst. An important catalytic effect is observed in all cases, and the maximum effect is reached for the sample containing palladium (in stoichiometrie substitution). From comparison of the various combustion temperatures, it is possible to deduce the following order of catalytic activity : "LMs" < "LMPts" < "LMPdn" < "LMRun" < "LMRus" < "LMn" < "LMPds". These results show that catalytic activity is influenced by two parameters : the presence of the substituted noble metal and the non stoichiometry. Soot/catalyst ratio : A series of experiments with different [soot/catalyst] ratios is carried out with stoichiometric substituted Pd doped perovskite as catalyst. Results show that the combustion temperature increases when the [soot/catalyst] ratio is higher than 15 wt%. This is probably due to the lack of contact between catalyst surface and all the soot particulates beyond this point. Catalyst ageing and specific area : Simulation tests on Pd containing catalyst in the presence of 5 wt % of soot are conducted in a furnace in the same conditions as for TG-DTA, from room temperature up to 800~ during 10 minutes, then an aliquot part of the sample is taken off, mixed with soot and tested in TG-DTA, whereas the remaining of the sample is kept in the fi~mace for further runs. The results (Table 2) show that catalytic reactivity is weakly influenced by ageing test despite the decrease of surface areas, the stabilization of which is reached after the third run. (Ethylene-glycol preparation gives the highest specific area mid activity.) Isothermal t e s t : H e a t i n g in TG-DTA up to the chosen temperature is performed under pure nitrogen which is then replaced by air for combustion. The sample is then heated at higher temperatures until the total combustion of soot is achieved. These experiments evidence that the combustion rate of soot increases with temperature, and that the carbon black can be totally and rapidly eliminated at a telnperature higher than 450~ whereas the liquid hydrocarbon part of the simulated soot is completely oxidized at 200~

568 Table 1. Screening test results. Catalysts are tested with 15 wt % soot

S~nbol Tcalc 1st DTA (~ %loss 64.0 Hydrocarbon Carbon Black (CB) 18.2 Stimulated Soot 600 25.0 Lao. 8Sro. 2MnO3 +~ LMs 600 20.0 La0.8Sro.2Mn0.91Fo.o903+~, LMn 20.0 Lao. 8Sr0.2Mno.999Pt0.0o 103+~ LMPts 600 23.3 Lao.8Sr0.2Mn0.9Pt0.0o8F0.o9203+~, LMPtn 600 16.7' Lao. 8Sro.2Mno. 9Ruo. 103+X LMRus 900 20.0 18.3' Lao.8Sro.2Mno.9Ruo. 103 +X LMRus 600 25.9 18.3' La0.8Sr0.2Mno.9Ru0.008F0.09203+~, LMRun 600 23.3 16.7" Lao.8Sro.2Mno.999Pdo.oolO3+~ LMPds 900 23.3 Sample

peak Tm 305 350 300 275 295 305 340 355 305 345 280 302 325 352

Lao.8Sro.2Mtk).9Pdo.oo8Fo.o9203+~,i LMPdn

900

16.7

307

Lao.8Sro.2Mno.999Pdo.oolO3+k LMPds l_zo.8Sro.2Mno.9Pdo.oo8Fo.09203+k LMPdn

600 600

20.0 18.3

260 290

2 nd DTA % loss 90.2 59.0 73.7 56.7 60.2 56.7 56.7

peak Tm 350 675 670 480 460 485 460

76.7

560

63.3

490

63.3

475

60.2

540

50.0* 8O.0 60.0 56.7

525 605 450 490

Tcalc "temperature of calcination, *" two DTA peaks. "s" indicated on symbol means a stoichiometric formula, and "n" is non stoichiometry 3.2. Characterization 3.2.1. XRD Carbon black : The XRD pattern (Figure 2) shows four wide peaks due to poorly crystallized graphite. These peaks correspond to the stacks of parallel hexagonal layer planes. Catalysts : XRD patterns indicate the existence of one phase which crystallizes in rhombohedral structure with the following parameters : a~7.7 5A and a~90.27 ~ (R3m).

569

Table 2 "Preparation method, surface area and ageing influence on the catalytic activity of the catalyst containing Pd "LMPds" calcined at 600~ The soot to catalyst ratio is 5 wt %. Preparation method

Test No

spec. area m2/~.

Ethylene-glycol solution

1 2 3 4

23.4 17.78 16.17 15.67

Aqueous solution

1st DTA peak* % wt loss Tm ~ 225 28 230 28 . . . 260 22

16.45

250

30

2

14.78

260

16

3 4

9.54 8.94

. 265

.

. 20

2nd DTA peak** % wt loss Tm ~ 445 70 480 62 . 455 75 460 65 490 85 500 60 600 81 . 470 62

* 9hydrocarbons oxidation ; ** 9carbon black oxidation.

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110

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Figure 2. XRD pattern of carbon black 3.2.2. TPD Several TPD analysis are carried out conceming carbon black, Pd containing catalyst and mixture of both of them. In the first sample (Figure 3.a), desorption of CO and CO2 was observed. CO2 desorbs at low temperature (200-400~ while CO desorption begins at 200~ to become important at 550~ CO and CO2 arise from surface carbon-oxygen complexes. The TPD curves of catalyst (Figure 3.b) show two important desorbed species : CO2 and 02. CO2 certainly results from the decomposition of residual carbonated components remaining during the preparation. 02 may

570

correspond to adsorbed and absorbed oxygen species on the perovskite structure [17]. When the catalyst is mixed with the carbon black, C02 and CO desorptions are observed while oxygen desorption disappears (Figure 3.c). (,o + I,M t,,,X

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-50

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400

600

Temperature, ~

Figure 3. NOx, HC and CO conversion profiles obtained over Cu-NaY during temperature programmed reaction at W/F-O. 15 gs/cm 3. For gas feed composition see Experimental (2.3).

613 conversion to be observed at lower temperatures, but data at 400~ show that lowering zeolite copper affects also the hydrocarbons conversion which decreases of 19% for both Cu-HZSM5 and Cu-NaY. Moreover, a remarkable effect of copper content on CO conversions is evident for the two zeolites. In particular, in the absence of copper the CO concentration at the outlet was higher than at the inlet reactor, due to the partial oxidation of hydrocarbons with oxygen. The presence of copper promotes the conversion of CO to CO2, up to reaching nearly total conversion at copper loadings corresponding to about 100% exchange level, but at lower temperatures over Cu-HZSM5 with respect to CuNaY. The catalytic activity of the over-exchanged Cu-HZSM5 sample (203% exchange level), evaluated at W/F - 0.05 gs/cm 3, resulted only slightly lower with respect to Cu-HZSM5 containing 3.28 wt% of copper.

4. DISCUSSION At variance of the laboratory data reported in [3, 6, 13], in the experimental conditions investigated by us for the selective reduction of NOx with the hydrocarbons at the engine exhaust gas neither HZSM5 nor NaY zeolite are active in converting NOx. Copper loading gives comparable activity to both zeolites for the selective reduction of NOx (about 30% conversion at 400~ The decrease of NOx conversion for temperatures higher than 400~ observed for all catalysts tested, can be attributed to the competition between NOx reduction by hydrocarbons and HC oxidation by oxygen, the latter becoming the predominant reaction when the temperature increases. It is well known that Cu-HZSM5 zeolites are much better catalysts for the direct decomposition of NO than other catalysts based on different zeolites. However, the lack of large differences in the catalytic performances of the two Cu-loaded zeolites investigated must be related to the specific features of the selective reduction of NOx with hydrocarbons, especially in the real conditions of the engine exhaust gas. Moreover the activity exhibited by the H form of ZSM5 and Y zeolites in the selective reduction of NOx [6, 13] requires the role of the transition metal to be understood, in comparison to that played in the direct decomposition of NO [2, 6, 14]. The analysis of the data in Table 2 shows that not all Cu sites are equivalent in their reducibility. Schematically, three different behaviours can be envisaged. A portion of Cu is easily reduced with He at 823 K, a second portion requires a treatment with CO at 773 K, a third one is unaffected by the reduction with CO, being still stable after the latter treatment, on ESR evidence. It is remarkable that

614 only Cu-HZSM5 samples with a copper content in the vicinity of 100% exchange contain Cu 2+ species which are reduced by the treatment with He at 823 K. The maximum fraction of Cu 2+ which can be reduced with He is roughly 20% of total copper. In all samples, after reduction with CO at 773 K, ESR spectra show file presence of a fraction of Cu 2+ which is not reduced by this treatment. In particular, 0.2 to 0.3 Cu wt% and 1.5 to 1.9 Cu wt% are the amotmts of Cu 2+ not reduced with CO in ZSM5 and Cu-NaY, respectively. Are these features in some

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Cu wtX Figure 4. A correlation between the molar fraction of Cu 2+ reduced in the treatment with He at 823 K (s Cu-HZSM5 and O, Cu-NaY) and the catalytic activity at 773 K for the NO decomposition (full line and dotted lme refer to CuHZSM5 and Cu-NaY respectively). Catalytic activity data (Rg, NO molecules converted to N2/s g, scale on the righ 0 are taken from ref [7]. way correlated to the catalytic activity in the selective reduction of NOx and in the direct decomposition of NO? Iaa a previous investigation of NO decomposition it was fotmd that the first addition of copper to ZSM-5, up to about 80% exchange level, leads to catalysts with rather low activity. Conversely, the activity of Cu-HZSM5 catalysts increases by roughly 100-fold, when the extent of copper exchange increases from 80 to 100%. At any Cu-exchange level, up to 100%, the catalytic activity of Cu-NaY is substantially lower compared to Cu-HZSM5. All these facts showed

615 that not all Cu sites are equivalent in their decomposition activity and that 20% is an upper limit for the fraction of Cu which is active in Cu-HZSM5 catalysts [7]. Considering further that a redox mechanism has been generally proposed for the decomposition of NO, the copper sites active for this reaction are only those endowed with the suitable redox properties. In view of the striking coincidence between the values reported above as upper limit for the active fraction of copper in Cu-HZSM5 on one side and the active fraction of Cu which is reduced during the treatment in He at 823 K on the other side (20% in both cases) we propose that the active copper is that reduced to Cu + during the treatment with He. This hypothesis is here substantiated by the correlation presented in Figure 4, where the molar fraction of the Cu 2+ reduced in the treatment with He at 823 K (data taken from Table 2) and the catalytic activity on Cu-HZSM5 and Cu-NaY (data from ref. [7]) are reported as function of the Cu wt%. In the case of the selective reduction with hydrocarbons the effect of copper content on the rate of NOx reduction has been evaluated from the low conversion data obtained at 300~ The rates increase with copper content (Table 3) and

Table 3. Catalytic activity (R~, NOx molecules/s g and RCu, NOx molecules/s Cuatom) at 573 K and W/F=O.15 g~cm3for the NOx reduction on C u - ~ 5 and Cu-NaY.

Catalyst(a)

Rg. 10-16

RCu. 106

CuZ-0.92 3.5 6.3 CUZ-3.28 7.2 3.7 CUZ-5.64 9.0 2.6 CUY-2.49 1.6 1.1 CUY-7.66 2.3 0.5 (a) CuZ=Cu-HZSM5, the figure atter CuZ and CuY specifies the Cu wt%. have similar values for both series of catalysts. The rates of NOx reduction nonnalised with respect to the total copper content are nearly independent of the Cu content, showing a slight decrease by increasing the Cu loading. The values for Cu-HZSM5 catalysts are only slightly higher than for Cu-NaY. This different behaviour with respect to the direct decomposition could be still related to a redox mechanism if one considers the comparable fraction of Cu reduced by the treatment with CO instead of the fraction reduced by He in CuHZSM5 and Cu-NaY. (Table 2). The alternative explanation is that a redox cation is not essential for the reduction of NOx with hydrocarbons [6, 14]. The marked dependence of the CO conversion on the type of zeolite and on the

616 copper content (Figures 2 and 3) indicates that the end product of hydrocarbons oxidation (CO or CO2) is strictly related to the redox cation. 5. CONCLUSIONS

The comparison of catalytic activity in the selective lean NOx reduction at the exhaust of a spark ignition engine has shown that similar performances in terms of NOx conversion can be obtained on Cu-loaded ZSM-5 and Y zeolites at 400~ Reaction rates of NOx reduction evaluated at low temperature (300~ and normalised with respect to copper atom resulted about five times higher for Cu-HZSM5 than for Cu-NaY. This behaviour is much different from that found on the same catalysts for the direct decomposition of NO, whose rate is strongly enhanced on Cu-HZSM5 in the range 80-100% of exchange level, with respect to Cu-exchanged Y zeolite. It has been proposed that the copper active for the direct decomposition of NO on Cu-HZSM5 is the last fraction of exchanged copper, which is reduced by He treatment at 823 K. A redox mechanism involving a much higher fraction of the exchanged copper could explain the lack of differences in the performances of Cu-HZSM5 and Cu-NaY zeolites. Moreover the conversions of CO on the two zeolites are somewhat different, suggesting that the redox Cu cation should play a significant role in determining the end product of hydrocarbons oxidation. ACKNOWLEDGEMENTS. The authors acknowledge Dr. G. Petrini of Enichem Anic for kindly supplying H-ZSM5 zeolite sample and Mr. G. Minelli for the chemical analysis. REFERENCES

1 2 3 4

W. Held, A. Konig, T. Richter and L. Puppe, SAE Paper 900496 (1990). M. Iwamoto and H. Hamada, Catal. Today, 10 (1991) 57. M. Iwamoto, H. Ftmficawa and S. Kagawa, in: New Developments in Zeolite Science and Technology, Proc. 7th Int. Zeolite Congr., Y. Murakami, A. Ijima and J. W. Ward (eds.), Kodansha, Tokyo, 1986, p. 943. M. Iwamoto, N. Mizuno and H. Yahiro, in : New Frontiers in Catalysis, Proe. 10th Intern. Congr. on Catalysis, L. Guczi, F. Solymosi and P. Trtrnyi (eds.), Akadrmiai Kiado, Budapest, 1993 p. 1285.

617 5 6 7 8 9 10 11 12 13 14

B.K. Cho, J. Catal., 142 (1993) 418. J.O. Petunchi, G. Sill and W. K. Hall, Appl. Catal. B, 2 (1993) 303. M.C. Campa, V. Indovina, G. Minelli, G. Moretti, I. Pettiti, P. Porta and A. Riccio, Catal. Lett., 23 (1994) 141. G. Moretti et al., to be published. C.D. Wagner, L. E. Devis, M. V. Zeller, J. A. Taylor, R. H. Raymond and L. H. Gale, Surf. Interf. Anal., 3 (1981) 211. R. A. Schoonheydt, Catal. Rev.-Sci. Eng., 35 (1993) 129. I. Jirka and V. Bosacek, Zeolites, 11 (1991) 77. E. Giamello, D. Murphy, G. Magnacca, C. Morterra, Y. Shioya, T. Nomura and M. Anpo, J. Catal., 136 (1992) 510. H. Hamada, Y. Kintaichi, M. Sasaki, T. Ito and M. Tabata, Appl. Catal. 64 (1990) L 1. M. Shelef, Catal. Lett., 15 (1992) 305.



619

OXIDATION STATE OF COPPER DURING THE REDUCTION OF NOx WITH PROPANE ON H-Cu-ZSM-5 IN EXCESS OXYGEN.

T. Pieplu, F. Poignant, A. Vallet, J. Saussey, J.C.Lavalley & J.Mabilon *+ Laboratoire catalyse & spectrochimie, CNRS URA 0414, ISMRA-Universitd, Bd A4~l Juin, 14050 Caen Cedex, France *Institut Francais du Pdtrole, B.P. 311, 92506 Rueil-Malmaison France.

ABSTRACT NO (reactant) and CO (product) molecules were used as IR probes of the copper oxidation state in H-Cu-ZSM-5 catalysts. CO adsorption is specific to Cux sites. Its characteristic band at 2158 cm1 provides quantitative results on integrating its molar extinction-coefficient (~) NO decomposes oxidizing CuI to CuE. Propane and oxygen in a special IR reactor cell always yielded chemisorbed CO. Use of a indicates the NO influence on Cu state.

1.1NTRODUCTION The removal of NO in exhaust gases of automobile equipped with gasoline engines has been sucessfidly performed by using the so-called three-way catalyst system. However, under conditions of substantial excess O2, the rate of reduction decreases markedly on this kind of catalytic system [1 ]. Therefore, de-NOx from the exhaust gases of diesel engines, which involves a substantial excess 02, is still an unresolved problem. Recently, it has been reported that N O can be

+ This work was supported by a Brite Euram project

620 reduced to N2 with hydrocarbons as reducing agents even in the presence of excess O2 using solid catalysts such as Cu-zeolites [2]. To improve the process which is not yet of practical interest, basic research on the copper electronic state in working conditions is needed. In this paper we report the results obtained by FT-IR spectroscopy on a HCu-ZSM-5 catalyst containing 2.5 wt% Cu. We first test in static conditions, whether reactants such as NO or products like CO are able to discriminate between Cu ' and Cu" oxidation states. Then the results are applied under working conditions using a special IR cell acting as a reactor.

2. EXPERIMENTAL The H-Cu-ZSM-5 catalyst was prepared by cationic exchange with Cu(NO~)~ solution. From the following data Si/AI=16.8 and 2.48 weight % of copper we deduce the amount of alulninium: 5.39 A1/unit cell e.g. H5.4-2nCUn(II)A15.48i90.6O192 and then the amount of copper: 2.31 Cu/unit cell. Thus, the sample was labelled Cu-ZSM-5-17-85 i.e. the standard identification used in all publications. For IR measurements, the smnple was pressed into self-supporting discs (~10 lng.cm-~). The spectra of the adsorbed species were obtained by subtracting the spectrum of the wafer from the spectrum obtained after adsorption. Static experiments The wafer was placed in a cell, where it underwent all activation and adsorptive treatments in a strictly in situ configuration. Spectra were recorded at room temperature (hereafter denoted by r.t.) at a resolution of 4 cm-' on a Nicolet 5SX FT-IR spectrometer. Prior to spectral recording, samples were oxidised or reduced, according to the following procedures : (1) Oxidised sample (hereafter referred to as H-Cu-ZSM-5(Ox)) : First the smnple was treated twice as follows : oxygen (100 Torr) was admitted to the sample at 773 K for 1/2 h and evacuated for 1/4 h. Then, oxygen (100 Torr) was admitted to the sample at 773 K for 2 h. The sample was cooled to r.t. in the oxygen atmosphere, and O~ was removed by evacuation at r.t.. Evacuation of O~ at higher temperatures would result in a partial reduction of copper. (2) Evacuated sample (hereafter referred to as H-Cu-ZSM-5(Evac)) : After O~ treatment at 773 K as before, the sample was evacuated at 773 K ovemight and then cooled to r.t. under a dynalnic vacuum.

621 Dynamic experiments The cell design has already been reported [3]. It is installed in a continuous flow system built directly on the FT-IR spectrometer (Nicolet Magna 750) to minimize the dead volume. The cell can be considered as a gas flow reactor with a dead volume less than 0.2 cm 3. Those capabilities perlnit reactivity experiments, combined with rapid IR spectroscopic lneasurements of surface species to be made in a maimer which has not been possible in standard IR cell. The GC collection was perforlned with a Delsi chrolnatograph on line. Gases were also analysed by FT-IR in a short spacial cell, also directly com~ected to the IR cellreactor, with a Nicolet 5SX spectrometer. NOx reduction was measured as the ratio C% = (NO ~ 100/NO ~ Prior to spectral recording the sample was treated, according to the following procedure : the catalyst was heated progressively to 623 K (2.5 K.min-') under O: (5 %) in He and maimained for 3 hours in these conditions (calcination). It was then exposed (under flow: 25 cm~.min-' ; GHSV = 50000 h-') to different previously analysed gas mixtures.

3. RESULTS AND DISCUSSION 3.1 Static experiments

The spectra of H-Cu-ZSM-5(Evac) and (Ox) are presented in Figure 1. Both spectra show v(OH) bands at 3740 and 3610 Cln-' corresponding to silanol and acidic Si-OH-A1 framework groups. Moreover, overtones and combination bands of the framework vibrations are situated at 2000, 1850 and 1620 cln -'. Moreover, the spectrum of H-Cu-ZSM-5(Ox) shows a broad band between 3750 and 3200 cm-' and a sharper one at 1620 cln-' whereas the intensity of the 3610 cm-' band is higher for H-Cu-ZSM-5(Evac). Subtracted spectra clearly evidence two absorptions near 3750-3200 and 1620 cm-'. Owing to the fact that the 3610 cm-' OH band intensity is weaker after oxidation, the broad band in the v(OH) range presents a window at this wavenumber. These features are explained by taking into account the reversibility of the copper oxidation state change according to the pretreatment or the nature of the surrounding atmosphere. The concomitant equilibrium of charges when reducing the sample would be assured by the water coordinated on Cu ~ which gives rise to H + ions increasing the BrOnsted acidity under reduction conditions (these protons provide the charge equilibrium). Thus, study of the v(OH) bands intensity can be used as a lneans to determine the variation of the copper oxidation state.

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3.1.1 CO adsorption OmLI-Cu-ZSM-5(Evac) successive introduction of CO portions at r.t. leads first to a v(CO) band at 2158cm -~ characterising CO adsorption on Cu ~ sites [4]. A very weak broad is also noted at 2110 cm -~ ; it corresponds to the same species with ~CO contained in natural abundance. As in the case of the parent sample, no CO adsorption on Si-OH-A1 groups is observed at r.t.. When the equilibrium pressure reaches 1 Torr, another band is observed at 2177 cm -~ A shoulder is also noted at 2151 cm -1 (Figure 3a). They both increase in maison (Figure 2) at the expense of the 2158 cm -~ band. They could be due to CO adsorption on Cu ~ sites [5].

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To check the assigmnents, CO has been adsorbed on H-Cu-ZSM-5(Ox). Figure 3b shows that CO adsorption is in such a case very low 9only a weak band at 2158 cln-' is observed when first portions are filtroduced whereas the two bands (2177, 2150 cm-') appear under CO pressure. Their weak intensity discards the possibility of CO adsorption on Cu" sites. We prefer to assign the 2177, 2151 cm-' couple to gemdicarbonyl species adsorbed on Cu ~sites [6]. It seems from the literature, that Cu'(CO): species have never been reported before. However, gemdicarbonyl species have been observed on oxidized transition metals like Ni § [7] and Pd+[8]. It has been seen that the 2177, 2151 cm-' couple disappears on evacuation at r.t., restoring the 2158 cm-' band corresponding to irreversibly chemisorbed species. In all cases (especially with H-Cu-ZSM-5(Evac)), for the first portions of CO introduced, it has been checked that all CO is totally chemisorbed. Moreover, there is a linear variation between the intensity of the 2158 cm-' band and the amount of CO hltroduced (Figure 4). This allows us to deduce the integrated molar extinction coefficient" ~co = 13.5 cm.~tmol-1

624 It appears that CO is able to characterise the presence and the number of Cu ~ sites. By contrast, it does not adsorb on Cu ~ sites. The weak bands observed on H-Cu-ZSM-5(Ox) are due to a few (about 5 % of the total copper content) Cu' residual sites persisting even after oxidation. Such a result is in agreement with [9] reporting that Cu" sites are very easily reducible, as shown by results obtained under pure oxygen or O~ + He mixture. As for the H-Cu-ZSM-5(Evac) catalyst, from the intensity of the 2158 cm-' band observed after the hatroduclionof a amount of CO followed by evacuation at r.t., it appears that CO detects only 1.4 Cu§ cell, e.g. 60 % of the total copper amount. This confirms literature results [2] reporting that CO does not detect all the copper sites. Note that if Cu ~ were present, a v(CO) band below 2100 cm-' should appear [10]. 40

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Fig. 4 - Determination of the integrated molar extinction coefficient of v(CO) band at 2158 cm". 3.1.2 NO adsorption Nitric oxide does not adsorb on the parent H-ZSM-5 sample. Introduction of a small amount of NO on H-Cu-ZSM-5(Evar leads mainly to one band at 1811 cm-' due to Cu§ species. Increasing the NO amount leads to a more complex spectrmn showing 4 main bands : 1811 cm-' (Cu§ 1826 and 1 7 3 3 ClTI"1 (Cu+('NO)2) and 1907 cm-' (Cu:+-NO) [11] (Figure 5a). At r.t. the intensity of the latter increases with time, at the expense of the others, indicating the oxidation of some Cu ~sites into Cu" sites.

625 Introduction of a small amount of NO on H-Cu-ZSM-5(Ox) mainly leads to the 1907 cm-' band ; however a small one is observed at 1811 cm" showing that not all the copper sites were completely oxidised like in the case of CO adsorption. Note that a spectrum similar to that observed on H-Cu-ZSM-5(Ox) is obtained when a large amount of NO is introduced on H-Cu-ZSM-5(Evac) and remained in contact with the catalyst for 1 h at r.t..

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Whatever the oxidation state of the catalyst two other bands are noted at 2232 (weak) and 2133 cm-' for large amounts of NO introduced. They are assigned to N:O and NO2 + chemisorbed species, respectively [12]. When 02 is introduced on a small amotmt of NO adsorbed on the oxidized sample (Figure 5b) other bands appear at 1629, 1597 and 1574 cm-'. Hall et al. assigned the first one to NO: adsorbed species [13], whereas the other two would be characteristic of nitrate species [ 14]. Although NO is able to differentiate Cu ~ and Cu ~ sites, complex spectra are often observed (Cf figure 5b, spectrttm C) due to the formation of N:O and NO:. Moreover, even at r.t., NO oxidizes Cu I sites into Cu ~ sites and therefore cannot be used as a probe molecule for the characterisation of the copper site oxidation state.

626 3.2 Dynamic experiments The method has been applied to study the NO reduction (2000 ppm) by propane (2000 ppm) at 623 K in the presence of an excess O: (5 %) under helium flow. Before the study of this complex reaction, preliminary experiments have been performed using only two reactants. 3.3.1 Propane + oxygen Under flow, in steady conditions, the propmle conversion is 60 %. Olfly CO: and H:O are detected by gas chromatography. The spectrum of the species formed on the catalyst is presented in Figure 6. Water formation explains the broad band between 3700 mid 3000 cm-'. CO is chemisorbed on Cu ' sites as shown by the sharp band at 2156 cm-'. From its intensity, one can estimate that the amount of Cu t is 2.7 % of the total copper amount. The strong bands between 1625 and 1400 cm -~ correspond to carboxylate species. O.Og] 0.03~ I 0.07-~ O. 06-j, 4

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3.3.2 Propane + nitric oxide After 30 min of time-on-flow, the propane conversion is 4.4 % and that of NO is 3 %. The products formed are CO: and N:O as observed by IR spectroscopy. No H:O nor NO: has been detected as reaction products. As soon as the C~H~ + NO mixture is introduced, subtracted spectra (Figure 7) show a negative absorbance between 3700 and 3500 r -~ with a positive sharp band at 3610 cm-' indicating a reduction of some Cu ~ sites into Cu ~ sites. Although CO is not detected as a

627 product, the sharp band at 2158 cm -' indicates that a small amount of CO is formed and remains chemisorbed on Cu' sites. This confirms the catalyst reduction. Weak bands are observed in the v(CH) range. The high wavenumber of some of fllem (3060 cm-') eharacterises the formation of ethylenie species. Another band is noted at 2047 em-' and tentatively assigned to fulminate species [15]. With time on-stream the propane oxidation and NO~ reduction decrease. A new species is formed, eharacterised by a band at 2248 em-', assigned to isocyanate species [16]. The intensity of ethylenie v(CH) bands and those at 2248 and 2047 cm-' increase with time-on-flow whereas that at 2158 cm-' decreases. Since the spectrum in the v(OH) range does not change, the intensity decrease of the v(CO) band at 2158 cm-' does not correspond to a partial reoxidation of the catalyst but rather to partial poisoning of Cu' sites by more stable species.

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3.3.3 Propane + oxygen + nitric oxide NO addition in propane and oxygen flow increases up to 68 % propane oxidation whereas NO reduction reaches 45 %. This result shows a positive effect of NO in propane oxidation in agreement with recent work on H-ZSM-5 reporth~g that addition of small amounts of NOx drastically increases the propane conversion [17]. This suggests a direct reaction between propane and NOx. One of the O: roles would be to eliminate strongly chemisorbed species evidenced under propane and NO flow, without O: ; such species could poison active

628 copper sites. No CO is detected in the products but, again, a band is observed at 2158 cm" (Figure 8), characteristic of CO adsorption on Cu' sites. Its intensity is weaker thin1 that observed under flow without NO. This weaker intensity, the study of the ,,(OH) bands indicating no catalyst reduction and the increase of propane combustion are in favour of a more oxidized copper state.

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IR spectra obtained under flow conditions always present a band at 2158 cm-' due to CO formation and adsorption on Cu ' sites. Its weaker intensity when introducing NO in the propane + oxygen flow shows that Cu ~ sites are predominant in reaction conditions. Since the NO conversion in the presence of propane without oxygen is very low, one of the oxygen effects would be to maintain the catalyst in a high oxidation state, favouring the reaction. Another role would be to avoid the surface poisoning. Our method with gas flow reactor combined with rapid IR spectroscopic measurements of surface species permits detection of some species adsorbed on the working catalyst (carboxylate, isocymlate). Future experiments would determine whether some of these species could be intermediates in the NOx reduction by propane.

629 REFERENCES

8

9 10 11 12 13 14 15 16 17

Held, W. ; KOnig, A. ;Richter, T. ; Puppe, L. SAE Paper 900496 Iwamoto, M. ; Mizuno, N., Yahiro, H. Sekiyu Gakkaishi 1991, 34, 375. Joly, J.F. ; Zanier-Szydlowski, N. ;Colin, S. ; Raatz, F. ; Saussey, J. Lavalley, J.C. Catal. Today, 1991, 9, 31. Huang, Y. Y. J. Catal. 1973, 30, 187. Fu, Y., Tian, Y., Lin, P. J. Catal. 1991, 132, 85. Lavalley, J.C. et al, to be published. Kermarec, M. ; Olivier, D. ; Richard, M. , Che, M. J. Phys. Chem. 1982, 86, 2818. Lokhov, Y. A. ; Davydov, A. A. Kinet. Katal. 1980, 21, 1523. Hall, W. K., Li, Y. J. Catal. 1991,129, 202. Ghiotti, G. ; Boccuzi, F. ; Chiorino, A. Stud. Surf. Sci. Catal. 1985, 21,235. Giamello, E. ;Murphy, D. ; Magnacca, C., Shioya, Y. ; Nomura, T. ; Anpo, M. J. Catal. 1992, 136, 510. Chao, C.C. ; Lunsford, J.H.J. Amer. Chem. Soc 1971, 93, 71. Valyon, J., Hall, W. K. J. Phys. Chem. 1993, 97, 1204. London, J. W. ;Bell, A. T. J. Catal. 1973, 31, 32. Nakamoto, K. Infrared and Raman spectra of inorganic mad coordination compounds ; 4 ~ Ed., Wiley Interscience Publication ; 1986, 289. Ukisu, 9 Y. ; Sato, S. ; Muratlnasu, G. ; Yoshida, K. Catal. Lett. 1991, 11,177. Sasaki, M . , Hamada, H. ; Kintaichi, Y. ; Ito, T. Catal. Lett. 1992, 15, 297.




631

NO D E C O M P O S I T I O N OVER PARTIALLY REDUCED M E T A L L I Z E D CeO2 C O N T A I N I N G C A T A L Y S T S . Gangavarapu R a n g a Raoa, Paolo Fornasierob, Jan Ka~parb, Sergio Merianic, Roberta Di Montec and Mauro Grazianib alnternational Centre for Science and High Technology, Padriciano 99, 34100 Trieste (Italy); bDipartimento di Scienze Chimiche, Universitdt di Trieste, Via Giorgieri 1, 34127 Trieste (Italy); CDipartimento di Ingegneria dei Materiali e Chimica Applicata, Universitdt di Trieste, Via Valerio 2, 34127 Trieste (Italy).

ABSTRACT M/CeO2-ZrO 2 (M=Rh,Pt) solid solutions are investigated as catalysts for the reduction of NO by CO. It is shown that incorporation of CeO 2 into a ZrO 2 framework strongly promotes the reduction of the metallized support. The reduced support efficiently decomposes NO suggesting a direct participation of the support in the NO conversion.

1.INTRODUCTION

NO removal by reduction with CO is a key step in the catalytic conversion of autolnotive exhaust. Rhodium is extensively added to the commercial catalysts to promote this reaction and the high NO conversions and selectivity towards N 2 formation which are observed over rhodium catalysts compared to other noble metals, are generally associated with its ability to dissociatively chemisorb NO [1]. The effectiveness of cerium oxide in improving the three-way catalyst performances is well established and it is ascribed to the following effects of the promoter: i) stabilization of metal dispersion [2] and of alumina support [3], ii) promotion of the water-gas shift reaction [4] and iii) enhanced oxygen storage and release by shifting between CeO2 under oxidizing conditions and Ce203 under reducing conditions respectively [5]. Recently, the oxygen vacancies associated with reduced ceria in the proximity of noble metal particles have been suggested as promoting sites for NO and CO conversions [6-7].

632 One of the major concern of the actual three-way catalysts is their thermal stability since, due to the close-coupled locations of the converter, the temperature of the catalyst may exceed 1200 K in the driving conditions. Upon ageing at such high temperatures, deactivation of the catalyst may occur due to sintering of metal particles, fonnation of irreducible rhodium species and collapse of the A120 3 surface area. In addition, the Oxygen Storage Capacity (OSC) of the CeO 2 promoter strongly decreases upon thermal ageing, due to the growth of CeO2 crystallites and/or formation of CeA103 [8]. It was shown that addition of ZrO2 to the washcoat significantly improved the thermal stability of the catalyst by hindering the sinterization of the CeO2 particles [9]. This suggests that a close interaction between CeO2-ZrO 2 may thermally stabilize the CeO 2 promoter. Incorporation of CeO2 into a solid solution with ZrO2 might provide a suitable way to improve the thermal resistance of the CeO2 component due to the ceramic nature of these ceramic alloys. Furthermore, in the solid solution, the undesirable decline of the OSC due to fixation of the Ce3+r Ce 4+ redox couple in the 3+ state (CeA103, Ce2(SO4)3) should be limited. On the basis of these considerations we decided to investigate a number of CeO2-ZrO 2 ceramic alloys as supports for noble metal catalysts for the reduction of NO by CO. Here we report clear evidence for NO decomposition occurring over reduced ceria containing catalysts, suggesting a possible new role of both the metal and ceria promoter in the three-way catalysts under transient conditions. Temperature Programmed Reduction (TPR) experiments show that incorporation of ZrO2 into a solid solution with CeO2 strongly enhances the reduction of the metallized smnples which occurs in the bulk of the support at fairly low temperatures. As a consequence, a strong dependence of the reduction behaviour upon the structural properties of the solid solution is also observed.

2.EXPERIMENTAL

CeO2-ZrO2 solid solutions with CeO2 content ranging from 10% to 90% were prepared by firing mixtures of the oxides at 1873 K for lh (surface areas = 0.51.5 m2g-1). Powder x-ray diffraction analysis (Siemens Kristalloflex Mod.F Instrument, Ni-filtered CuKa) showed presence of pure fluorite type structure for CeO 2 molar contents greater than 60%. For lower CeO 2 contents, tetragonal TZ ~ and TZ' phases [10] were detected. Supports were impregnated with RhC13.3H20 or Na2PtC16.nH20 to incipient wetness, then the catalysts were dried at 393 K overnight and finally calcined at 723 K for 5 h. Temperature Programmed Reduction was carried out in a COlwentional system at a heating rate of 10 K min -1. H 2 consumption in the TPR was estimated by using CuO as a

633 standard. Oxygen Storage Capacity was measured by pulse technique in the same equipment used for tile TPR experiments. The samples were reduced in H2/Ar mixture (10 K lnin -1 to 700 K and then held for 2 h). H2 was then desorbed in Ar flow (20 ml min-1) at 700 K for 2h. The oxygen uptake was measured by injecting pulses of 02 (0.092 ml) into the flow of Ar passing over the catalyst (0.04-0.05 g) until the breakthrough point was attained. Catalytic experiments were carried out in differential conditions using a U-shaped glass micro reactor (NO (2%) in He, total flow 15 ml rain-1 or NO (1%) and CO (3%) in He, total flow 30 ml min-1, GHSV = 12500-50000 h-l). The effluents of the reactor (NO, N2, N20, CO and CO2) were analyzed gaschromatographically.

3. RESULTS AND DISCUSSION 3.1 X.R.D. and Temperature Programmed Reduction Characterization of the Samples According to the cerium content, the ceria-zirconia ceramic alloys exist in three different phases, namely monoclinic, tetragonal and cubic [ 11 ]. Below 1300 K the monoclinic and cubic phases appear to be thermodynamically stable, however, when the ceramic method is employed for the synthesis of the solid solution, metastable tetragonal phase is easily formed in a wide compositional interval and it is fairly stable at ordinary temperatures [10c]. In our synthesis we have used a non quenching cooling rate which produces two phases of tetragonal symmetry referred as TZ ~ mad TZ'. These phases exist pure in the compositional range 520% CeO2 and 40-60% CeO2 respectively, while at CeO2 content 20-40% a mixture of TZ ~ and TZ' is obtained. The former phase is characterized by a larger ortogonality (c/a = 1.018) compared to the TZ' phase (c/a ~ 1.010) [10b]. As showaa in Fig. 1, powder X.R.D. spectra confirmed formation of solid solutions in the present samples. The d(111) linearly decreases in the cubic region with decreasing CeO2 content due to the smaller Zr4+ ionic radius (0.80 A) compared to Ce 4+ (0.97 A). In the range of composition 30-40% of CeO2, the constant values of (hkl) spacing indicate that a two phase region is present as expected on the basis of the phase diagram. Consistently, both Ceo.3Zro.70 2 mad Ceo.4Zro.602 are mixtures of respectively TZ ~ (77 and 22%), TZ' (17 and 67%) and cubic (6 and 11%). All other samples present a single phase composition. Reduction behaviour of all the samples was investigated by means of Temperature Programmed Reduction. TPR profiles of the Ceo.6Zro.40 2 sample as well as Rh and Pt/Ceo.6Zro.402 samples are compared in Fig.2 with those carried out on pure CeO 2 and Rh/CeO2 samples.

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Figure 1. (111) spacing as determined by powder X.R.D. of CeO2-ZrO 2 solid solutions. They show a strong promotion of the reducibility of the Ceo.6Zro.40 2 solid solution in the presence of noble metals as shown by the appearance of a strong reduction feature between 500 and 700 K in the TPR profiles of both supported Rh and Pt/Ceo.6Zro.402 catalysts. This feature is absent in the other samples and it is associated with a partial bulk reduction of the support. By using the Mooi and Jolmson model [12], 0.5 ml H 2 g-1 can be estimated for surface reduction of a 1.0 m2g -1 surface area CeO 2 sample and 0.7 ml H 2 g-1 are estimated for the reduction of the Rh203 precursor. A consumption of about 1.3 ml H 2 g-] is measured for the peak at around 350 K (Fig.2, traces 2,4) which is consistent with occurrence of Rh203 and surface reduction. In the range of temperatures 500-700 K, a consumption of 9.5 ml H2 g-1 is estimated for the reduction process depicted h~ Fig.2, trace 4, which gives a bulk composition of Rh/Ce0.6Zr0.40].9. Therefore the support reduction can be associated with the formation of anionic oxygen vacancies in the bulk of solid solution due to the reducible Ce 4+ cation. This is supported by magnetic susceptibility measurements which showed close coincidence between the degree of reduction as estimated from TPR and that estimated according to [13] from this teclmique by considering that only Ce 3+ contributes to the lnagnetic moment. The absence of the feature centered at 700 K

635 in the tmmetallized samples (Fig.2, trace 3) indicate that support reduction is promoted by metal particles which spill H 2 over the support. The importance of H 2 spill-over in facilitating the reduction of CeO2 has long been recognized. Generally speaking, CeO2 with a surface area higher than 20-30 m2 g-], shows presence of two reduction peaks approximately at 770 K and 1100 K which have been associated respectively with surface and bulk reduction [5]. In the presence of supported metal, the latter feature shifts to lower temperatures and splits into several peaks. At variance with this, TPR profile of low surface CeO2 samples is almost unaffected by the presence of supported metal particles.

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Figure 2. TPR profiles of (1) Ce02, (2) 0.5%Rh/Ce02, (3) CeOo.6Zro.402, (4) 0.5%Rh/CeO0. 6Zro.402 and (5) 0.5%Pt/CeO0. 6Zro.402 . The observation that bulk reduction is promoted upon incorporation of CeO2 into a solid solution with ZrO 2 prompted us to investigate the dependence of the reduction behaviour upon structural properties of the samples. Fig.3 shows the TPR profile of a series of Rh/CeO2-ZrO2 samples with mnount of CeO2 between 20% and 100%. It appears clearly that forlnation of a solid CeO2-ZrO2 solution even at relatively low ZrO2 contents strongly promotes bulk reduction of the support, as new feature -hereinafter indicated as LT (Low Temperature) peakbelow 1050 K is observed. Moreover, in the cubic phase, the maximum of the

636 peak broadly shifts towards lower temperatures upon decreasing the CeO2, while the reverse is observed in the tetragonal region. The relative magnitude of the LT peak centered at 600-840 K and that of the one centered at 1050-1250 K hereinafter indicated as HT (High Temperature) peak- is also affected by the amount of CeO2 in the sample. On decreasing CeO2 content, the HT peak becomes smaller and broader, and it is almost nihil in the tetragonal samples. Reduction of CeO2 is suggested to proceed initially via a surface reduction and then on increasing the temperature bulk reduction occurs through a lattice oxygen diffusion limited process [13]. Quantitative estimation of the degree of reduction showed that after LT peak, a bulk composition of Rh/CemZrl_mO x (0.2 < m < 0.9) with 1.87 < x < 1.92 is obtained. In the fluorite oxides, for defect

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300

500

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I

700

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Figure 3. TPR profiles of calcined (1) Rh/Ceo.2Zro.802; (2) Rh/Ceo. 4Zro.602; (3) Rh/Ce o.5Zro. 50 2(TZ') ; (4)Rh/Ce o.5Zro. 50 2(cub ic), (5)Rh/Ce o. 6Zro. 402, (6) Rh/Ceo.sZro.202, (7) Rh/Ce02.

637 concentration above 2-x=0.08, the activation energy for the mass transport increases with increasing defect concentrations [14a]. This suggests that the defects which form in the course of the reduction might clusterize [14], which makes the oxygen transport more difficult, and this is responsible for the appearance of the HT peak. A full discussion of the reduction and reoxidation behaviour is reported elsewhere [ 15]. There is another very important point which should be noted: the occurrence of a bulk reduction also promotes the Oxygen Storage Capacity of the present samples as measured by oxygen uptake in comparison to Rh/CeO2 catalysts irrespectively of their surface area. For example, after a reduction at 700 K, a Rh/Ceo.5Zro.502 sample of surface area 1.5 m2g -1 showed, at the same temperature, an oxygen uptake of 9.0 ml 02 g-1 compared to 4.8 ml 02 g-1 measured on a Rh/CeO2 sample (surface area 130 m2g -1) [15]. In summary, the observed reduction behaviour shows that incorporation of ceria into a solid solution with zirconia strongly favours formation of reduced Ce 3+ species, and there is an optimum range of composition (CeO2 = 40-60%) where the highest degree of support reduction and lowest reduction temperatures are observed. Finally, the 60 K shift of the LT peak toWard lower temperature observed over the cubic Rh/Ceo.5Zro.502 sample in comparison with the tetragonal one (Fig.3, traces 3,4) is an indication that in the cubic structure the reduction process is favoured due to the higher oxygen mobility in the bulk.

3.2 Catalytic Activity Measurements In order to investigate the effects of the nature of the support on the catalytic properties of the present catalysts, selected catalytic runs were carried out in a flow reactor at 473 K. The effects of the initial degree of reduction of the support were also analyzed and therefore prior to the catalytic ran, the catalysts were reduced both at 473 K and 673 K for 2h. As indicated from the results of the TPR experiments, after a reduction at 473 K, no significant reduction of the bulk of the support is obtained while after a reduction at 673 K, a significant fraction of the bulk of the support is reduced. Consistently, separate TPR experiments showed that after an isothermal reduction at 473 K, the magnitude of the LT peak appears unaffected, while after an isothermal (2h) reduction at 673 K, the LT feature is no long observed. Notably, in the latter experiment carried out over the Rh/Ce0.6Zr0.40 2 sample, after the isothermal reduction we measured a degree of reduction very close to that obtained after the LT peak.

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Figure 4. NO (,) and CO (Jr) conversions over Rh/Ceo.6Zro.40 2 prereduced respectively at 673 K (a) and 473 K (b). Typical CO and NO COlwersion profiles as a function of time on stream at 473 K are reported in Fig.4b. At this temperatures N20 is the major nitrogen containing product. For all the catalysts employed we observe an initial partial deactivation of the catalysts to reach a stationary state after approximately 5-6 h which is consistent with previous studies [16]. Recently, we observed over a Rh/A120 3 catalyst that at a reaction temperature of 473 K in the presence of NO and CO, oxidative disruption of the supported rhodium particles to give isolated R h I sites is favoured while higher temperatures favour reductive agglomeration [17]. This suggests that upon steaming at 473 K, rhodium particles might be disrupted decreasing the efficiency of the catalysts as a result of smaller particle size. The effects of steaming, however, appear affected by the reducing pretreatment. As shown by NO conversion over the Rh/Ce0.6Zr0.40 2 catalyst prereduced at 673 K (Fig.4a), while the CO conversion shows only a slight decrease with time on stream, the NO conversion show an unusual behaviour showing a rapid initial deactivation which is followed by a slight increases of the activity starting at about 80 min of reaction and peaking at 200 min. Then, the NO conversion slowly decreases to the steady state value after approximately 6-8 hours of reaction. No such unusual behaviour was observed over the Rh/Ce0.6Zro.40 2 catalyst prereduced at 473 K (Fig.4b). The influence of the pretreatment temperature on the NO conversion becomes more apparent when the reaction rates measured in steady state conditions are reported in an Arrhenius fashion (Fig.5).

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Figure 5. Apparent Activation Energies for NO (o) - CO (m) Reaction over Rh/Ceo.6Zro.40 2 prereduced respectively at 673 K (a) and 473 K (b). There is a clear inflection point at 500 K in the Arrhenius plot of NO reaction rate over the Rh/Ce0.6Zr0.402 catalyst prereduced at 673 K which is absent both in the CO reaction rate over the same catalyst and in the CO and NO reaction rates over the catalyst prereduced at 473 K. From the former plot an apparent activation energy for NO conversion of 64 kJ tool-1 is obtained for NO conversion below 500 K, while a value of approximately 120 kJ mo1-1 is measured for all the other cases. This suggests that for NO conversion a complementary mechanism of lower activation energy is operating in the samples in which the support is initially reduced in the bulk, which is not observed when only rhodiuln and the surface have been reduced in the catalyst pretreatment. A possible interpretation of the low activation energy path observed for NO conversion is that dissociation of NO is occurring over Ce 3+ sites. There are, indeed, some indication in the literature about the ability of reduced ceria to be reoxidized by oxygen containing moieties such as H20 [18], CO2 [18,19] and NO [20]. As shown in Fig.5, NO is promptly decomposed at 473 K giving N2 and N20 over the M/Ce0.6Zr0.40 2 (M=Pt,Rh) catalysts prereduced at 673 K while this reaction is ahnost negligible over the catalyst prereduced at 473 K. Noteworthy is that NO decomposition is achieved also over the pure Ce0.6Zr0.40 2 support prereduced for 2 h at 1073 K i.e. at a telnperature where the support reduction is appreciable even in the absence of the metal. No 02

640

A12

4

0

0

100

200

300

Reaction Time (min) Figure 6. NO Decomposition at 473 K over (11) Pt/Ce 0 6Zr 0 40 2 and (J) Rh/Ceo 6Zro ,t02 prereduced 673 K; (~) Rh/Ceo_6Zr 0 402 prereduced 473 K~md (-~) C-eo.6Zro.402prereduced 1073 K " evolution was detected which indicates that the reduced support is reoxidized by the oxygen liberated in the reaction. Consistently, the 02 uptake calculated from the NO conversion was, within 7% error, equivalent to the H2 consumption in the reduction (02 = 1.6 10-3 equiv g-]; H2 = 1.5 10-3 equiv g-]). The observation of the occurrence of NO decomposition over pure support, of course, do not rule out the role of the metal in dissociating the adsorbed reactant. As a matter of fact the NO conversion curves reported in Fig.6, show a different time dependence. At 473 K, the main product of both CO-NO and NO decomposition reactions is N20 while N 2 is the main reaction product at high temperatures. Rh effectively dissociates NO compared to other platinum metals and this suggests that different N20 selectivity should be observed over the catalysts examined. A selectivity of about 80-85% in N20 was observed in the experiments reported in Fig.6, which suggests that, in these conditions, the role of the metal in the dissociation of NO might be limited. The inflection point in the Arrhenius plot (Fig.5) can be associated with a complete bulk reoxidation of the catalysts. Consistently, a Temperature Programmed Oxidation of the Rh/Ceo.6Zro.402 prereduced at 673 K and using NO as oxidant, showed a single peak with maximum at 490 K. Very

641 importantly, ma apparent activation energy of 67-68 kJ mo1-1 was measured in this experiment over both Rh/Ceo.6Zro.40 2 and Ceo.6Zro.402 . There is a further point of interest in these experiments. Surface oxygen vacancies, produced by a reductive treatment of CeO2 have been suggested as promoting sites for NO and CO conversions. Recently, we observed that CO2 hydrogenation over Rh/CeO2 catalysts is promoted by a high temperature reduction and the observed transient rate enhancement was associated with formation of oxygen vacancies located at the periphery of the metal particles which in tum facilitate CO2 dissociation [19]. Generally speaking, all these investigation point out the important role of surface oxygen vacancies [3,6,7,19] or surface oxygen nests [21] in determining the catalytic behavior of M/CeO2 systems. Recent evidence, however, shows that even long range effects involving bulk CeO2 lattice oxygen may play important role in these phenomena. CO TPD from a Rh/CeO2 catalyst showed that migration of lattice oxygen from CeO 2 to the metal occurs [22]. The oxygen storage capacity was increased by formation of a La203-CeO2 solid solution in Pt, RI~La203-CeO2/A1203 catalysts which was attributed to formation of lattice oxygen vacancies due to La 3+ incorporation [23]. Maire et al [24] recently observed an enhancement of rate of CO oxidation in the presence of prereduced Pt/CeO2 catalysts which was attributed to the presence of bulk oxygen vacancies. Participation of lattice oxygen has been recognized in several oxidation reactions while the present results suggest that the bulk oxygen vacancies may play an important role of in promoting the rate of the oxygen exchange reaction also in the reduction.

4. CONCLUSIONS

Metallized CeO2-ZrO2 appear to be potentially interesting materials for automotive catalysts as the incorporation of CeO2 into the solid solution strongly promotes the reducibility of the support which occurs in the bulk at moderate temperatures. Consequently, these materials exhibit a high Oxygen Storage Capacity notwithstanding the low surface area of the present samples. The present observations also point out a new mechanism for the role of ceria in the reduction of nitrogen oxide attributable to the presence of redox couple Ce3+Ce 4+, which, at least in the low temperature regimes, effectively dissociates NO. In view of these results, an altemative explanation may be suggested for the increased conversion of a wet exhaust compared to dry conditions [4]. In the presence of water, both CeO2 and the supported metal efficiently catalyze the water gas shift reaction producing H2 which then may be

642 spilled-over the support by the supported metal. The Ce 3+ sites thus produced, efficiently decompose NO and are reoxidized to Ce4+. ACKNOWLEDGMENTS.

Ministero dell'Universit~ e acknowledged for financial support.

della Ricerca

Scientifica

(Roma)

is

REFERENCES

10 11 12 13 14

K.C.Taylor, in "Catalysis-Science and Teclmology", (J.R.Anderson and M.Boudart, eds.), Springer-Verlag, Berlin, 1984, vol.5. J.C.Sununers and S.A.Ausen, J.Catal. 58 (1979) 131. B.Harrison, A.F.Diwell, and C.Hallett, Plat. Met. Rev. 32 (1988) 73. G.Kim, Ind.Eng.Chem.Prod.Res.Dev. 21 (1982) 267. H.C.Yao and Y.F.Yu Yao, J.Catal. 86 (1984) 254. J.G.Nunan, H.J.Robota, M.J.Colm, and S.A.Bradley, J.Catal_ 133 (1992) 309. a) A.F.Diwell, R.R.Rajaram, H.A.Shaw, and T. J.Truex, in "Catalysis and Automotive Pollution Control II", Stud.Surf.Sci.Catal. (Crucq, A. ed.), Vol. 71, pp.139-152, Elsevier, Amsterdam, 1991; b) G.Munuera, A.Femandez, and A.R.Gonzalez-Elipe, ibidem, pp.207-219. J.Z.Shyu, W.H.Weber and H.S.Gandhi, J.Phys..Chem. 92 (1988) 73. M.A.Harkonen, E.Aitta, A.Lahti, M.Luoma, T.Maunula, SAE 910846 (1991). a) S.Meriani, Mat.Sci.Eng. 71 (1985) 369; b) S.Meriani and G.Spinolo, Powder Diffraction 2 (1987) 255; c) S.Meriani, Mater.Sci.Eng. A109 (1989) 121. A.E.McHale, Phase Diagrams for Ceralnists, Almual 1991, p.20. M.F.L.Jolmson and J.Mooi, J.Catal. 103 (1987) 502; erratum: J.Catal. 140 (1993) 612. A.Laachir, V.Perrichon, A.Badri, J.Lamotte, E.Catherine, J.C.Lavalley, J.E1 Fallah, L.Hilaire, F.le Nonnand, E.Quemere, N.S.Sauvion and O.Touret, J.Chem.Soc. Faraday Trans., 87 (1991) 1601. a) J.A.Killner and B.C.H.Steele, in "Non Stoichiometric Oxides" (O.T.Sorensen, ed.), ch.5, Academic Press, New York (U.S.A.), 1981; b) H.Matzke, ibidem ch.4; c) C.R.A.Catlow, ibidem ch.2.

643 15 16 17 18 19

20 21 22 23 24

P.Fomasiero, R.di Monte, G.Ranga Rao, J.Kagpar, S.Meriani, A.Trovarelli and M. Graziani, J.Catal. 151 (1995) 168. W.C.Hecker and A.T.Bell, J.Catal. 84 (1983) 200. J.Ka~par, C.de Leitenburg, P.Fomasiero, A.Trovarelli, and M.Graziani, J.Catal. 146 (1994) 136. K.Otsuka, M.Hatano, and A.Morikawa, J.Catal. 79 (1983) 493. A.Trovarelli, G.Dolcetti, C.de Leitenburg, J.Kaspar, P.Finetti, and A.Santoni, J.Chem.Soc., Faraday Trans. 88 (1992) 1311; A.Trovarelli, G.Dolcetti, C.de Leitenburg, J.Kaspar,, J., in "New Frontiers in Catalysis", Stud.Surf.Sci.Catal. (L.Guczi, F.Solymosi, and P.Tetenyi, eds.), Vol.75, pp.2781-2784, Elsevier, Amsterdam, 1993. R.K.Hertz, Ind.Eng.Chem.Prod.Res.Dev. 20 (1981) 451. M.G.Sanchez, and J.L.Gazquez, J.Catal. 104 (1987) 120. G.S.Zafiris and J.Gorte, J.Catal. 139 (1993) 561. T.Miki, T.Ogawa, M.Haneda, N.Kakuta, A.Ueno, S.Tateishi, S.Matsuura, and M.Sato, J.Phys.Chem. 94 (1990) 644. C.Serre, F.Garin, G.Belot, and G.Maire, J.Catal. 141 (1993) 9.


A. Frennet and J.-M. Bastin (Eds.) Catalysis atwl Automotive Pollution Control 111


645

S E L E C T I V E C A T A L Y T I C R E D U C T I O N O F N O x IN D I E S E L E X H A U S T G A S E S WITH NH3 OVER Ce & Cu M O R D E N I T E A N D V 2 0 5 / T i O 2 / W O 3 T Y P E C A T A L Y S T S : C A N Ce S O L V E T H E NH3 S L I P PROBLEM? R.J. Hultermansa, E. Itoa, Jr. J6zsefb, P.M. Lugta and C.M. van den Bleeka

aDepartment of Chemical Technology and Material Science, Delft University of Technology PO Box 5045, 2628 BL, The Netherlands bDepartment of Chemical Technology, Technical University of Budapest Budafoki ut 8, 1521 Budapest, Hungary ABSTRACT The performance of two zeolite type catalysts on their NOx-SCR activity and their SO2 oxidative activity is compared to a vanadium type catalyst. Home made Ce&Cu mordenite and a commercially available V205/TiO2/WO3 type catalyst have been tested for NOx reduction with ammonia in model and diesel exhaust gases. The Cu mordenite catalyst showed good performance from 300 to 550~ However, SO3 formation was detected starting at 400~ and selectivity loss caused by oxidation of NH3 to NO starting at 450~ The vanadium type catalyst showed the same behaviour as Cu mordenite; selectivity decline above 450~ and SO3 formation above 400~ However, the Ce mordenite catalyst showed high temperature (>400~ activity without oxidation of SO2 to SO3 and NH3 to NO; a large excess of NH3 resulted only in a limited NH3 slip.

1.INTRODUCTION

In the last few decades a lot of attention has been paid to diesel engine emission reduction. Particulary soot and NOx emissions have been the subject of extensive research trying to obtain reductions by engine and fi~el modifications and various aflertreatment devices. This paper is aimed at the development of an aftertreatment device for NOx control: selective catalytic reduction of NOx using an injection of ml aqueous urea solution. This tecMique stems originally from the field of power plant NOx control and as such is proven to be quite effective [1]. Because of safety reasons and ease of use, urea is preferred over NH3 [2-4]. The

646 main problem in applying this technique to non-stationary engines (HD trucks) results from the fact that the exhaust gases vary widely and rapidly in temperature as well as in NOx content. This means that the catalyst must be active in a wide temperature range and one must be very well able to control the amount of urea injected The temperature of diesel engine exhaust gas varies somewhere between 100 600 ~ Catalysts so far used in power plants can be used from about 300 450~ The lower limit is determined by ammonia sulfate formation, the upper limit by NH3 oxidation and catalyst stability. The limit at low temperature is less severe when using low sulfur fuel. Furthermore, most diesel engines don't produce much NOx at low loads and the relative importance of such low loads/low temperature conditions is fiulher diminished by the weighting criteria used in standard road tests, e.g. the 13-mode test procedure [5]. An additional phenomenon at high temperatures is the formation of SO3, thereby increasing the particulate emission. Essentially a SCR aftertreatment system should posses the following characteristics: 1) SCR activity, also at high temperatures, 2) no SO2 oxidation activity and 3) no ammonia slip. l.l.Temperature window A lower temperature limit will be set at 300~ Using urea injection at lower temperatures, polymerisation products can be formed. Furthermore, at these temperatures ammonium sulfate formation will block most SCR activity. The temperature range in which the catalyst will have to work is consequently from about 300~ to 550~ Standard vanadium type SCR catalysts have an upper temperature limit of about 450~ Above this temperature conversion drops rapidly as a result of ammonia oxidation and at even higher temperatures deactivation follows. For developing new catalysts zeolite type catalysts were chosen; new developments showed a very high SCR activity for a combination of CuH-MOR & H-MOR in a temperature window of 200 - 600~ [6].

1.2.SO2 oxidation In this paper much attention is paid to an effect which is typical for diesel engine exhaust; the implications of the presence of sulfur in diesel fuel with regard to using catalysts. These implication can roughly be divided into two parts: the effect on the particulate emission and the effect on SCR activity. The sulfur in diesel fuel is mainly converted to SO2. An increase in particulate emission would be caused by catalytic oxidation of SO2 to SO3 over the SCR catalyst. Since SO3 forms aerosols, this is being detected as particulates. The second effect is deactivation of the SCR catalyst by poisoning (p.e. ammonitun sulfate formation).

647 Standard diesel fuel contains up to 0.3 wt % sulfur. In the near future this will be limited to 0.05 wt % [5]. This sulfur is converted mainly to SO2 (more then 95 %), and the remainder leaves the engine as SO3, H2SO4 mist, or some other oxide form. About 1-3 percent is collected during the EPA transient test cycle as H2SO4 mist [7]. All oxidation catalysts tend to catalyse the oxidation of SO2 to SO3. Especially vanadimn and platina type catalysts are well known SO2 oxidation catalysts. For a commercial or newly developed SCR catalyst, this is undesirable. Because the emission of particulates is increased, an estimation is needed of the particulate emission caused by SO3 formation [7,8]: particulates :

0.1 * % S u l p h u r * % S 0 2 conversion

It can be calculated that for a 5 percent SO2 oxidation rate using a low sulfur fuel (0.05 wt %) the resulting additional emission of particulates would be 0.03 g/kWh. Since the near future emission limit is 0.15 g/kWh it is clear that SO2 conversion should be low. The exact amount depends of course on the weighting factors applied for the high load points in the testing procedures. In the literature [8] a related source of SO3 emission is described: sulfur storage. This is the effect that stored sulfur on a catalyst support is released during a temperature transient. When oxidation catalysts (Pt on g-A1203 or SiO2) are subjected to aging (typically 300 hours) the amount of particulates during an EPA transient cycle increases drastically. The way to handle this problem is using a support that doesn't store sulfur (SiO2).

1.3.Ammonia slip Ammonia slip typically occurs when overstoichiometric amounts of urea/ammonia are injected. Due to the ammonia storage capacity of the catalyst this is not emitted directly so if an appropriate control action is taken, ammonia slip can be avoided. However, up to today an inexpensive and fast NOx and/or ammonia sensor is not available to accommodate such a control action. Solutions have been proposed in the use of engine maps for predicting the NOx output [9] and/or an additional oxidation catalyst for avoiding ammonia slip [3]. The latter is detrimental to the sulfate emissions and as most of the oxidized ammonia will leave the system as NO, the overall NOx removal efficiency will be lowered. Therefore, it would be convenient if a possible overdose of ammonia will leave the system in the form of nitrogen (N2). This would solve the SCR control problem. 2.EXPERIMENTAL For initial catalyst screening purposes a standard laboratory flow setup was used. Typical test gas compositions for the catalyst activity tests were 1000 ppm NO and NH3, 5% 02 and balance Argon. An initial screening on SO2 oxidizing

648 capacity was performed. The Cu-MOR and Ce-MOR were first pressed and then crushed again to yield a particle diameter range of 0.3-0.7 mm. Catalyst preparation and characterization is documented by Ito et al [10]. Normally 0.5 gram of catalyst was used with a Oow of 500 Nml/min; this corresponds with a space velocity of about 35 000 h "~. A VG Prima 600 type Mass Spectrometer was used to measure all nitrogen containing species and SO2. Further testing was performed with a somewhat larger apparatus (30 times larger; 15 grams of catalyst and 15 N1/min). With this setup it was also possible to use diesel exhaust gases. Gas mixtures consisting of NO, NH3, 02, H20 and SO2 in balance Nitrogen or air were used. The diesel exhaust gas composition used was 7 % 1-120, 7 % CO2, 50 ppm SO2, 10 % 02, 570 ppm NOx, balance nitrogen [ 11 ] with 600 ppm NH3 added for the reaction. The diesel exhaust gases were filtered to remove any particulates. Two home made metal exchanged zeolite type catalysts were tested: Cu-MOR and Ce-MOR. A V2Os/TiO2/WO3 catalyst, the Degussa AG DN 32 washcoated monolith (300 cpsi), was fitted into the reactor which had an internal diameter of 1.95 cm. Somewhat more of the DN 32 catalyst, 24.8 versus 15.0 grams, was used to obtain the same space velocity. The NOx concentration was measured with an Eco Physics chemiluminescence NOx analyser. Ammonia was measured with a Siemens MIPAN (Microwave Process ANalyser). In case of dry model gases the disappearance of SO2 was measured with a Siemens Ultramat 5E NDIR (Non- Dispersive Infra-Red) analyser. In case of diesel gases SO3 was measured with a Severn Science Instruments automatic titration unit and the SO2 concentration was calculated on basis of the fuel sulfur content. Two diesel fuels have been used. The first one was a certified fuel, Haltermann CEC RF-03-A84, containing 0.14 wt % sulfur. The second fuel was a low sulfur fuel, obtained from van Gelder Aardolie B.V., with less than 0.001 wt % sulfur. In the case that certified fuel was used, the MIPAN ammonia analyser was equipped with an SO2 scrubber. 3.RESULTS AND DISCUSSION 3.1.Screening results of Cu & Ce-MOR The reduction of NO and the oxidation of 502 as a fimction of temperature using Cu-MOR and Ce-MOR was studied (Figure 1 & 2). The activity of CuMOR for the SCR reaction synthetic gases is very high; 100 percent conversion is already reached at 200~ Increasing temperature leads to a conversion drop which is probably caused by ammonia oxidation (the ammonia conversion was 100 percent). The Ce-MOR reaches this conversion level at 300~ A decline in NO conversion is found which is also attributed to ammonia oxidation. Behaviour of other, comparable, zeolite type catalysts in model gases are reported by Ito et al [10]. 502 oxidation occurs for Cu-MOR at about 400~ and leads at higher temperatures to excessive sulfate production. The Ce-MOR catalyst however,

649 only shows a little amount of oxidation at 600~ It should be noted that for practical purposes, especially in the low temperature range, it is possible to use far less Cu-MOR to reach the same conversion as the Ce catalyst.

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3.2.Catalyst testing with diesel exhaust

The next step was testing these catalysts with diesel exhaust gases. It was expected that activities would be lower because of the presence of water and sulfur compounds. This effect is shown in Figure 3, where, compared to the results from Figure 1, the onset of the SCR reaction shifts at least 100~ towards the high temperature region. For the Cu-MOR catalyst enough activity was retained in the desired temperature range, the Ce-MOR catalyst did lose some of its activity in the range of 300 - 400 ~ This could be attributed to a combination of reversible deactivation of water and an irreversible deactivation of sulfur compounds (Figure 4). Partial regeneration was possible by heating up the catalyst, so the sulfur compounds can be desorbed. As already stated by Ham (11) ammonium sulfates can be found in Cu-MOR pores at temperatures up to 400~ The Cu-MOR did also show some deactivation at temperatures below 300~ but because of the much higher activity a high conversion level is retained. In Figure 3 the DeNOx performanceof the vanadium catalyst is also given. It 40 + Cu-MOR should be noted that comparison with the Ce-MOR zeolite type catalysts is somewhat 30 o complicated because the vanadium A E catalyst is already put on a monolith Q. ~20 carrier. However, what can be seen is the o.j o characteristic behaviour of a vanadium (n catalyst" it starts to work well above 10 300~ (also because of ammonium sulfate formation) and shows an activity 0 decline at 450~ because of ammonia 350 450 250 550 oxidation. The sulfate production of this type of Temperature ( * C ) catalysts, Figure 5, follows the same trend as depicted in Figure 2; at about Figure 5:S03 production of DN 32, 400~ the vanadium type catalyst and Ce-MOR and Cu-MOR in diesel Cu-MOR start producing sulfates whereas Ce-MOR does not produce any exhaust using 0.14 wt % sulphur sulfates. One might expect no ammonium containing diesel fuel. sulfate formation when the catalyst does not oxidize SO2. However, the deactivation in a diesel exhaust or in model gases occurs at a much lower temperature than when SO2 oxidation is observed. Summarizing, a Ce-MOR catalyst is under development which does show a high activity over a wide temperature range. It should however be noted that, especially in presence of SO2, in diesel exhaust gases this temperature window is decreased significantly starting at about 400~ However, an important advantage is that no sulfates are formed. For practical purposes in diesel engine exhausts it will be necessary to use this catalyst in series with for example copper mordenite catalyst as already proposed by Medros [6]. Without physical separation and/or careful optimization with regard to catalyst activity, some sulfates will be

65i produced. Furthermore, since most zeolites tend to absorb large amounts of 502, in practise some temperature transient related desorption effects can be expected.

3.3.Ammonia slip

The main technical problem for application of SCR in transient operation lies in the control of the amount of ammonia/urea injected as explained before. Consequently, attention must be paid to the ammonia oxidative capacity of the catalysts. As can be seen in Figure 6 and 7 Ce-MOR does not produce any NO during SCR operation or ammonia oxidation whereas the vanadium type catalyst (and also the Cu-MOR) start to produce NO at higher temperatures. The question is wether it is possible to use an overstoichiometric amount of ammonia to reduce the NOx. The idea is that superfluous ammonia will be oxidized to nitrogen rather than NO. This would facilitate the control problem considerably and possibly make an additional oxidation catalyst superfluous. As can be seen in Figure 8 this works in a diesel exhaust gas at high temperatures. Of course, the amotmt of overdosing is not unlimited because the onset of ammonia oxidation may also shit~ to a higher temperature in case of diesel exhaust. Furthermore, chances of ammonia slip caused by desorption due to temperature transients will increase because more ammonia will be stored on the catalyst.

1.0

1.0

0.5

0.5

~E ~

~ 1.0

1.0

o~ 0.5 .~ E

o.s o

o

o.o

_

o.o

Temperature (*C)

Figure 6: NO and NH3 conversions during SCR operation (A), NH3 conversion and NO formation during ammonia oxidation ( o ) f o r DN32. The mixture used was 500 t~pm NH3 (& NO) in air, sv 35 000 h -~ .

o.o

o.o

Temperature (~

Figure 7: NO and NH3 conversions during SCR operation (A), NH3 conversion and NO formation during ammonia oxidation (o) for Ce-MOR. The mixture used was 500 ppm NH3 (& NO) in air, sv 35 000 h- 1.

652 4.CONCLUDING REMARKS 1.0

9

1.0

It has been shown that a metal exchanged mordenite (Ce) can have a high SCR activity without oxidizing 0.7 0.7 SO2 to SO3 and NH3 to NO. The main o o problem to be solved for diesel exhaust Z is the activity in the temperature region of 300-400~ This problem is less 0,4 0.4 when using low sulfur fuels. Until then, 200 400 600 800 1000 the Ce catalyst can only be used in high NH= in (ppm) temperature applications or for diesel exhaust in combination with other compounds (i.e. copper). Figure& Behaviour of Ce-MOR m The problems with the control of the diesel exhaust using low sulfur fuel as a urea injection can be avoided when the function of NH3 concentration, 440~ dosing needs not to be very precise. (,4) and 530~ The advantage of the Ce catalyst is that ammonia oxidation forms only nitrogen so relieving the control considerably. Until now, ammonia slip is oxidized (in most cases to NO) by placing an oxidation catalyst behind the SCR system. ACKNOWLEDGEMENT

The authors would like to thank the Dutch Ministry of Housing and Environment (VROM) for their financial support.

653 REFERENCES

9

10

11 12

H. Bosch and F. Janssen, Catal. Today, 2 (1988) 369. C.M. van den Bleek, P.J. van den Berg and A.G. Montfoort, 466, Second European Conference on Environmental Technology, Amsterdam, The Netherlands, 1987. H.T. Hug, A. Mayer and A. Hartenstein, SAE Paper 930363. A.W. Wypkema, PhD thesis, Del~, The Netherlands, 1991. CONCAWE, Motor vehicle emission regulations and fuel specifications 1992 update. ,rep. no. 2/92, Brussels, Belgium, 1992. F.G. Medros, J.W. Elridge, and J.R. Kittrel, Ind. Eng. Chem. Res. 28 (1989) 1171. K.J. Springer, Journal of Engineering for Gas Turbines and Power, 111 (1989) 361. D.J. Ball and R.G. Stack, 337, Catalysis and Automotive Pollution Control II, Amsterdam, The Netherlands, 1991. J. Walker and B.K. Speronello, SAE 921673. E. Ito, R.J. Hultermans, P.M. Lugt, M.H.W. Burgers, H. van Bekkum and C.M. van den Bleek, this conference, Catalysis and Automotive Pollution Control III. D.M. Heaton, TNO-MEL report 733030013, Delt~, the Netherlands. S.W. Ham, H. Choi, I.S. Nam and Y.G. Kin, Catal. Today, 11 (1992) 611.




655

REACTION STUDY OF DIESEL EXHAUST GASES OVER COPPER O X I D E B A S E D M O D E L C A T A L Y S T S

C.M.Pradier w H.VikstrOm, and J.Paul

KTH/Royal Institute of Technology, Physics III, S-1 O0 44 Stockholm, Sweden w correspondance ABSTRACT Nitric oxide reduction by hydrocarbons over oxidized copper samples has been studied by multiplexed mass-spectrometry in an all quartz reactor operated in static mode. At 600~ the reaction proceeds exclusively via consumption of HC and NO. NO is not consumed in the presence of dioxygen but preoxidation of the copper sample is necessary to facilitate high conversion rates. Infrared spectra obtained in situ at 45- incidence angle verify the conversion and show that the bulk of the active catalyst consists of cuprous oxide. A combination of IRand mass-spectroscopy has proven to be a successful way to identify additional products and intermediates in the gasphase.

1.1NTRODUCTION

The catalytic conversion of NO is a subject of great importance due to the environmental impact of the gas. New legistration, which puts stem limits on the emission from automobiles, has recently been proposed in the United States as well as in a number of European countries. This forms a new incentive to find economically attractive and efficient catalysts. The platinum group metals are extensively used in commercial catalysts for Otto engines but one major drawback with these metals is their high cost. Another shortcoming of these conventional three- way catalysts is their limited ability to operate under the oxidizing conditions of lean burn gasoline engines and diesel engines. Various materials containing copper have shown activity for NO reduction under these conditions but sulphur poisoning and deactivation by moisture limit their use [1 ]. Our approach is based on model studies where we isolate and characterize

656 different parts of the overall reaction scheme. The present work concentrates on NO/HC reactions under reducing conditions. With our ongoing project we will achieve a better understanding of the mechanisms involved on the metal and the metal oxide surfaces. This knowledge will be applied to tests under oxidizing condtions, mimicing the exhaust gas composition, with a higher yield and an improved process as the result. The materials aspects of the active catalyst are discussed elsewhere [2]. A new deposition method for copper oxide with alumina as the carrier relates to our model studies of the unsupported catalyst and has proven to be superior to conventional impregnation methods [3].

2.EXPERIMENTAL 2.1.Mass-spectroscopy A commercial quadrupole mass spectrometer (Balzer 421) was used to obtain information about gas conversion and consumption during the reaction. The sample was a 50 cm 2 disc of high purity copper (Goodfellow). Different gas mixtures, containing oxygen, nitric oxide, and isobutane, were tested in order to find optimal conditions for NO conversion. The sample and gas mixture (total pressure 5-10 torr) were heated in an all quartz batch reactor by an external oven. This arrangement mimics realistic reactor conditions with a gas-temperatm'e close to the catalyst's temperature, a condition rarely fullfilled in surface science experiments. A small amount of gas was continously removed through a pipe to the mass spectrometer. The activity of the empty reactor, including thermal decomposition and combustion, has been studied and found to be negligible. Kinetics were evaluated from mass spectrometric data without considering the thermalization factor.

2.2.1nfrared Spectroscopy Specular reflection Fourier transform infrared spectroscopy, performed with the beam striking the sample at 45- from the surface normal, was also used for in situ studies of the catalytic reaction. This technique makes it possible to observe changes in the gasphase composition [4-5]. The broad band reflectivity of the overlayer can be used to obtain the composition of a thin oxide film [6]. Infrared spectra have been obtained from polycrystalline samples and from Cu(110). The former samples are akin to the ones used for mass spectrometric studies. Distinguished from those studies our FTIR work was performed with a reaction vessel at room temperature. The sample was in this case resistively heated by tantalum wires. This combination separates the gas temperature from the temperatm'e of the catalyst. The temperature of the impinging molecules is a

657

complicated function of the sample temperature and the pressure in the pressure range >10 -3 torr. At this pressure the mean free path of molecules is shorter than the distance between the sample and the walls of a typical ultra high vacuum system integrated with a catalytic reactor.

3.RESULTS AND DISCUSSION

,/

I .

0

10

~

30

40

50

60

.

.

.

70

4

-

80

lime(rain)

Fig.1. Multiplexed mass-spectra from a sampling device in the batch reactor. The period to the left is characterized by preoxidation of the sample and consumption of oxygen and the period to the right by a simultaneous decrease of NO and isobutane and increase of nitrogen, water, and carbon dioxide. The reaction temperature was 600~ Figure 1 shows the gas-composition as a function of time during the preoxidation period and during typical batch mode conversion of NO and isobutane to nitrogen, water, and carbon dioxide. Small quantities of other products: carbon monoxide, other nitrogen oxides, and hydrocarbons, were also detected. These data were obtained from the all quartz reactor with a polyerystalline copper sample. The initial total pressure was 10 torr with a O2:NO:iso-C4H~o ratio of 1:5:10. Preoxidation occurs during the transitory stage of the reaction. This stage is characterized by the rapid consumption of oxygen and by the growth of a cuprous oxide overlayer [2]. NO and HC conversion start during this stage but leads to incomplete oxidation of HC to CO and HzO. The bulk structure of the

658 active catalyst is further investigated by X-ray diffraction following an extensive reaction cycle [2]. The transitory stage is followed by a stationary phase with a constant and higher rate of NO conversion. We measured the rate of conversion during this stationary stage. These data give a yield of 2 NO molecules converted per second and adsorption site. This value should be taken as a nominal number rather than an absolute value due to the lack of an independent evaluation method for the number of available adsorption sites. The above number was calculated from the number of copper atoms in a closely packed planar metal surface. 04H10

during reaction

,Jj

! OO2

,

H20

4000

CO2

H20

3000

2000

Wavenumber (crn-1)

1000

Fig. 2. Infrared spectra obtained by reflection off the sample in the reactor vessel, before and during the reaction. The incidence angle was 45 ~ and the intensity was measured in the specular direction. The qualitative conversion was confirmed by infrared spectroscopy (Figure 2). IR- spectra show the formation of gasphase intermediates in addition to the mare products: Nz, CO2, and HzO. These intermediates were ethylene, propene, and methane. The high incidence angle, 45-, is suitable to follow changes is the oxidized overlayer rather than to detect surface intermediates [2]. The optimum conditions for rapid conversion are sensitive to the temperature and to the sequence of gases introduced into the reactor, in addition to the relative pressures. Too low temperatures and too oxidizing conditions following the preoxidation period result in continous oxide growth [2]. Other erronous conditions result in carbon build-up and passivation or runaway oxidation with extensive internal generation of heat [2]. On the other hand,

659 considerably lower conversion temperatm'es with maintained high yields have been observed by in situ FTIR as a result of a gradual decrease of the externally supplied heat, once the converter is operating. The above quoted high yields at lower temperatures may correspond to the enhanced yields at constant temperatm'e, observed after regeneration cycles. Regeneration cycles by calcination were applied at regular time intervals for rich blends. The partial pressure of NO remains constant when the ratio Oz:NO is higher than 1:30. Each regeneration period is characterized by a reoxidation period with no NO consumption, during which oxidation of the copper sample or of surface residues occur. Removal of surface residues, mainly carbon, can be diagnosed by increased amounts of CO and CO2. As the oxygen is consumed, the NO reduction rate again approaches the same level as during previous cycles. The decrease of the NO partial pressure sometimes shows an oscillatory behavior followed by a very rapid decrease. The above observations in combination with unavoidable changes in the gas composition, due to the rapid rates and a limited vessel volume, give that the optimum conditions are limited to a narrow temperature and gas-composition window. Nevertheless, the high yields observed under the present optimal conditions and the likelihood of stable operation at lower temperatures are most encouraging. These yields are not out of range with conventional catalysts based on rare metals and compare favourably to complex oxides and zeolites.

4.CONCLUSIONS

Copper, modified by oxygen, was shown to be an active catalyst for reducing NO in the presence of a hydrocarbon. It is a realistic alternative to noble metals. Oxygen is necessary during a preliminary step of the reaction. Subsequently, the reduction of NO is effective on an oxide surface without oxygen in the gas phase. Kinetics results i.e. the rate of NO consumption and the NJCO ratio in the products are strongly dependent upon the temperature of preoxidation of the catalyst. This result suggests that the reaction is sensitive to the oxidation state of copper in the superficial layers. This original experimental approach led us to the conclusion that in situ FTIR, combined with Mass Spectrometry, is the appropriate analysis technique for i) products, ii) intermediates, and iii) catalytically active surfaces.

660 ACKNOWLEDGEMENT

We acknowledge the joyful visit of John Robbins to our laboratory. He boosted our progress in this project. REFERENCES

Ertl G., Hierl R., KnOzinger H., Thiele N., and Urbach H.P., Appl. Surf. Sci. 5(1980)49. Pradier C.M., Robbins J.L., Liang K., Hoffmann F.M., and Paul J., (manuscript) Pradier C.M., Hall R.B., Myers G., Ohman L.O., and Paul J., (manuscript) Greenler R.G., Hahn R.R., and Schwartz J.P., J.Cat.23(1971)42. London J.W. and Bell A.T., J.Cat.31(1973)96. Wood B.J., Wise H., and Yolles R.S., J.Cat.15(1969)362.

A. F rennet and J.-M. Bastin (Eds.) Catalysis amt Automotive Pollution Control 111


661

SELECTIVE REDUCTION OF NOx WITH A M M O N I A OVER CERIUM EXCHANGED ZEOLITE CATALYSTS: TOWARDS A SOLUTION FOR AN A M M O N I A SLIP PROBLEM

E. Ito, R.J. Hultermans, P.M. Lugt, M . H . W Burgers, H. van B e k k u m and C.M. van den B leek 1

Delft University of Technology, Department of Chemical Technology andMaterial Sciences, Julianalaan 136, 2628 BL Delft (The Netherlands) ABSTRACT Cerium-exchanged ZSM-5 and mordenite showed a high NO conversion (> 70 %) and a high selectivity to N2 (> 97 %) at 300 - 600 ~ for NO reduction with ammonia in the presence of oxygen. Ammonia was found to be oxidized by oxygen over these cerium zeolite catalysts exclusively towards N2 without production of N20 and NO. NO reduction with up to 30 % excess of ammonia exhibited a high NO conversion and complete conversion of NH3 at 300 - 500 ~ at a gas space velocity of 12,000 h~. This offers a possible solution for the ammonia slip problem in a selective catalytic reduction (SCR) system with NH3. Strong NH3 adsorption up to 600 ~ and a high amount of adsorbed reactive NO species in associated with the redox property of cerium (Ce~/Ce TM) are assumed to be responsible for the high NO reduction activity of cerium exchanged zeolite cat~ysts.

1. INTRODUCTION

The removal of NOx from exhaust gases is an urgent issue, and environmental regulations are becoming more stringent than ever. The selective catalytic reduction (SCR) of NOx with ammonia is the teclmique, which was extensively applied in stationary NOx sources from the 1970s, wlfile the successful development of a threeway catalyst made it possible to reduce NOx in gasoline automobile exhaust.

1To whom correspondence should be addressed

662 Nowadays an intense focus is being placed on the development of a catalyst applicable in oxygen-rich conditions, aiming at cleaning of diesel exhaust or leanburn exhaust gas. After a promising report on Cu-ZSM-5 [1, 2], a variety of zeolite catalysts has been investigated for NOx reduction with hydrocarbons as reductants: Cu-ZSM-5 [1-6], Fe-ZSM-5 [7], Ce-ZSM-5 [8] and H + zeolites [9] mostly with ethene, propane or propene; and recently Ga-ZSM-5 [10] and Co-ZSM-5 [11 ] were reported to be able to reduce NOx with methane as a reductant. Ammonia-type reductants, which include ammonia, urea, cyanuric acid and different ammonium salts, have been applied so far mainly for stationary sources. The apparent preference for a hydrocarbon reductant for a mobile deNOx system is mainly based on the following reasons: (i) Hydrocarbons are always present in a combustion exhaust; (ii) Equipping mobile sources with an ammonia tank is considered unsafe; (iii) Ammonia-type reductants require a stringent injection control to prevent ammonia slip (< 5 ppm required [12]); (iv) Ammonia is found to be converted to NO and N20 at higher temperatures (> 400 ~ over various SCR catalysts like V205 [12 - 14], WO3 [13] and Cr203 [15]; (v) SO2 present in a combustion exhaust is often converted to SO3 to produce acidic particulates [ 13]. Nevertheless, ammonia-type reductants are generally much more effective for NO reduction than hydrocarbons, as seen in a comparison between different literature data at a given gas space velocity (GHSV) [16 - 18]. This is mainly ascribed to an intrinsic high reactivity of amanonia towards NOx species to produce a N~ bond as a direct consequence, ha contrast, ha the case of hydrocarbon reductants, two NO molecules should be eventually combined to produce N2 with an intervention of the reductant hydrocarbon. For instance, Iwamoto et al. [19] and Ukisu et al. [20] have proposed isocyanate as an fiatennediate formed from a hydrocarbon and NO over a copper-based catalyst, while Yasuda et al. have suggested organic nitro and nitroso compounds as intermediates over Ce-ZSM-5 [21]. These species are hereat~er expected to react with NO [19], or NO2 formed in a separate activation of NO with O2 [21], finally leadfi~g to N2 production. Such a complicated reaction route with plural steps is clearly subjective to many side reactions. A loss of reductant by combustion with oxygen is probably the largest side reactions in a hydrocarbon system, and it drastically lowers the reductant utilization for NO reduction. In contrast, ammonia is relatively unreactive towards oxygen. Focusing on the intrinsic effectiveness of ammonia-type reductants, we have been investigathag the application of a urea solution for the NO reduction in diesel exhaust. Since urea decomposes into two reductant molecules (ammonia and/or cyanic acid) above 300 ~ ha the presence of water, it can serve as a safe reductant reservoir. A high performance of urea solutions in NO reduction has already been reported in detail elsewhere [16, 22]. The other disadvantages remained to be solved are (iii) the ammonia slip, (iv) unfavorable ammonia oxidation to NzO and NO, and

663 (v) a high SO~ oxidation. Ammonia slip can be prevented in principle by a precise control of reductant injection to meet a maximum NOx conversion and a minimum ammonia slip. However, this is rather difficult, in particular, under the non-stationary operation conditions of vehicles, and the present process control is not at a stage of application yet. An alternative solution is the development of a catalyst, over which NO is converted with ammonia efficiently towards N2, and an excessively injected ammonia is converted selectively to nitrogen. Such a catalyst system enables the present control system applicable without concerns about an ammonia slip and tmdesirable production of NO or N20 from ammonia. In addition, such a catalyst is desired not to promote SOz oxidation. We have recently reported that cerium-exchanged mordenite (CeNa-MOR) is a highly active and selective catalyst for NO reduction with ammonia in oxygen-rich conditions [23]. We have fitrther fotmd that it oxidizes SO2 to a negligible extent [24, 25], and that it appears to fulfill the aforementioned requirements for an ideal NH3SCR catalyst. In the present paper, we will report on these aspects of ceriumexchanged zeolite catalysts. Furthermore, its surface interaction with two reactants, NO and NH3, is examined with the temperature programmed desorption (TPD) technique.

2. EXPERIMENTAL

2.1 Catalyst preparation Na-MOR (5iO2/A1203 = 13.1, PQ Zeolite), Na-ZSM-5 (SiOJA1203 = 40, Uetikon) and Na-Y (SiO~/A1203 = 5.2, Akzo) were obtained commercially. Cation exchange was carried out with 8 - 25 g of zeolite hi one of following metal salt solutions (1.5 1) at a given temperature for 5 - 20 h: 4.0 - 35 mM copper(H) acetate or 4.0 - 35 mM cobalt(H) acetate at room temperature, 3.9 mM iron(n) sulfate at 70 ~ 4.0 - 8.3 mM ceritun(III) acetate or 2.0 mM lanthantun chloride at 70 - 100 ~ Exchange stoichiometries (Na + and M n+) were confirmed on a charge equivalent basis for these samples; these were denoted as CuNa-ZSM-5(95), CeNa-MOR(71) etc., the number hi parentheses refers to the percentage of ion exchange. Partly H + exchanged cerium samples were prepared by an ion-exchange in 2.7 - 8.3 mM cerium(HI) sulfate solution at 50 - 100 ~ They were denoted as CeNaH-ZSM-5(17) and CeNaH-MOR(41), in wlfich H+ sites were present at 67 % and 5 1 % (exchange stoichiometry), respectively. H-MOR was prepared from fully exchanged NH4+MOR followed by an air calcfllation at 550 ~ for 24 - 48 h. Exchanged samples were checked with X-ray powder diffraction for crystallflfity, and elemental analysis was carried out with ICP-AES (Inductively Coupled Plasma Atomic Emission Spectroscopy) and AAS (Atomic Absorption Spectroscopy). A commercial

664 V2OJAI~O3 catalyst (DNll0, 10 wt% VzOs, Rhtne-Poulenc) was used for a comparison.

2.2 Catalytic reactions Catalytic reactions were carried out using conventional fixed bed reactors; a bench-top reactor BTRS-900 (Autoclave Engineers) or a home-made automated system. The reactant gases, NO (1024 ppm or 1 % in argon), NH3 (952 ppm or 1 % in argon) and 02 (20 % in argon) were commercially obtained (Scott specialty gases) and used without fitaher purifications. These gases were applied under the following reaction conditions: NO (465 - 1000 ppm), NH3 (465 - 1000 ppm) and 02 (1 or 5 %) in argon at a total flow rate of 400 - 500 ml/min. 0.5 - 1.0 g of a pelletized catalyst (d = 0.5 mm on average) was used in a quartz tube reactor. These test conditions give gas space hourly velocities (GHSV) between 12,000 and 30,000 h "1 based on the apparent bulk density of zeolite (0.5 g/cm3). After a catalyst pretreatment under argon at 200 - 300 ~ for 2 - 3 h, reactions were started, and the effluent gas was monitored using a mass spectrometer (VG Prima 600, VG Analysis) for NO (m=30), NH3 (m=17), N2 (m=28), N20 (m=44), NO2 (m=46) and H20 (m=18), or by a combination of two methods: chemiluminescence NOx analysis (Signal 4000; Signal) and liquid-phase NH3 analysis (AutoAnalyser; Technikon).

2.3 NH3-TPD (Temperature programmed desorption) NH3-TPD was performed over CeNa-, LaNa-, H-, and Na-MOR with 0.1 g of catalyst powder ha a quartz tube reactor surrounded by a heater, and the effluent gas was monitored by a conventional thennoconductivity (TCD) detector. Catalysts were first pretreated in nitrogen from room temperature up to 600 ~ at a heating rate of 5 ~ followed by dwellhag at 600 ~ for 5 - 10 h. Samples were cooled to 100 ~ under a N2 flow, and a pure NH3 (99.9%, Air Products) flow was admitted on the catalyst for 0.5 h. After flushing lfitrogen until obtaining a stable zero signal, TPD was started at a constant temperature increase of 5 ~ up to 600 ~ under nitrogen, and desorbed ammonia was monitored.

2.4 NO-TPD (Temperature programmed desorption) NO-TPD was carried out with CeNa-, LaNa-, H-, and Na-MOR in a similar manner as described hi the NH3-TPD section except for a maximum desorption temperature of 560 ~ The effluent gas was monitored by a mass spectrometer (MAT44; Varian) for NO (m=30), NO2 (m=46) and N20 (m=44) at a scan rate of 15 scans/min for each species.

665 3. RESULTS 3.1 NO reduction with ammonia in the presence of oxygen

NO reduction with ammonia was performed in the presence of oxygen over a variety of transition metals (Cu, Co, Fe and Ce) exchanged in ZSM-5 (Fig. 1). Iron and cerium turned out to be highly active at temperatures above 300 ~ Iron was, however, not fi,'ther investigated, considering its undesirable high SO2 oxidation feature [26]. As shown in Fig. 2, cerium-exchanged mordenite (Ce 5.66 wt%) was found to be more active than Ce-ZSM-5 (Ce 3.09 wt%), whereas CeNa-Y (Ce 9.67 wt%) showed only a poor activity in spite of its highest cerium content. As shown in Table 1, partly H + exchanged cerium-mordenite and -ZSM-5 were effective as well with much smaller cerium contents, suggesting a catalytic role of Bronsted acid sites. A comparison between cerium-, copper-mordenite and a commercial vanadium oxide catalyst illustrates declining activities of copper and vanadium oxide in the higher temperature range (Table 1) and, an undesirable N~O formation (Fig. 3). In contrast, there was no N20 production observed over cerium-exchanged mordenite. 1.00 0.80 '>

0.60 o.,o

~

8 ~

0.60 < 0.40 0.20 [

O.2O

0.00 200

~ e 300 400 Tempcrature

0.00 .

500

600

/ "C

Figure 1. NO reduction with ammonia over metal-exchanged ZSM-5: NO 1000 ppm, NH31000 ppm and 02 5 % at GHSV of 30,000 h ~. (~ CeNa-ZSM-5(95), (o) CuNaZSM-5(96), (e) CoNa-ZSM-5(69) and (A) FeNa-ZSM-5 (96).

200

.

.

.

300

.

.

400

Temperature

.

500

600

I "C

Figure 2. NO reduction with ammonia over different cerium exchanged zeolites NO 1000 ppm, NH~ 1000 ppm and 5% 02 at GHSV of 30,000 h -~. (o) CeNa-MOR(70), (l~ CeNa-ZSM-5(95) and (A) CeNa-Y(65).

666

Table 1 NO reduction with ammonia in the presence of oxygen" NO 1000 ppm, NH~ 1000 ppm and O~ 5 % at GHSV of 3 O,000 h 1. Catalyst

Metal content

(wt%) CeNaH-ZSM-5(17) 0.37 CeNa-ZSM-5(95) 3.09 CeNaH-MOR(41) 3.23 CeNa-MOR(70) 5.66 H-MOR CuNa-MOR(69) 3.74 V2OJAlzO3 5.60 e~

NO conversion (%)

200oc

300oc

400oc

500oc

600 ~

2 13 61 55 3 97 53

67 84 100 100 32 95 100

88 90 95 96 71 78 85

87 82 92 84 77 58 19

73 68 81 64 46 34 0

1.00

150

o.so

r

100

~ ~

...q

~o O

50
97)

83(>97)

1.3

82(n.d.)

100(>97) 100(n.d.) 100(>97)

1.6

81(63)

100(81)

n.d.: not determined

86(93)

87(n.d.)

100(n.d.) 100(n.d.)

668 3.4 NI-I3-TPD of CeNa-, LaNa-, H- and Na-MOR CeNa-MOR(58) and LaNa-MOR(57) exhibited a strong NH3 adsorption, showing its desorption continuing even at the final temperature of 600 ~ Low temperature NH3 desorption (200 - 300 ~ observed with all four mordenite samples is ascribed to weakly adsorbed armnonia on the mordenite matrix. Over CeNa- and LaNa-MOR, another peak was observed at 400 - 500 ~ which was attributed to NH3 coordinated to metal ions (cerium or lanthanum). A high temperature desorption (>_ 600 ~ was observed over CeNa-, LaNa- and H-MOR. It might be associated with Bronsted acid sites, which can be expected in lanthanide-exchanged zeolite as reported for La-Y [28] and Ce-Y [29]. The strong ammonia adsorption on CeNaMOR explains a zero reaction order in NH3 observed for NO reduction in the presence of oxygen at 300 ~ [26]. 3.5 NO-TPD of CeNa-, LaNa-, H- and Na-MOR NO-TPD was carried out with CeNa-MOR(58), LaNa-MOR(57) and HMOR, and desorption of NO and N20 was observed (Figs. 5(a) and 5(b)). A separate experiment with Na-MOR exhibited only a negligible amount of desorption products. As shown in Fig. 5(a), CeNa-MOR(58) exhibited two NO desorption peaks: one at 170 ~ and another large peak at 290 ~ Since LaNa-MOR(57) and H-MOR showed the peak at 170 ~ as well, it is probably related to Bronsted acid sites. CeNa-MOR(58) exhibited a substantial amotmt ofN20 desorption (Fig. 5(b)). N20 is a weak adsorbate, and reported to desorb below 200 ~ from copper-exchanged zeolite [30]. Therefore, N20 observed above 200 ~ is assumed to result from a reaction of NO species on the catalyst stu-face. The large NzO peak observed with CeNa-MOR(58) at arotmd 300 ~ appears to correspond to a large NO desorption peak at 290 ~ It indicates that NO desorption at 290 ~ is associated with NzO formation observed at 300 ~ N20 formation on bulk cerium oxide was reported by Niwa et al. [31 ]. NO2 was not fotmd during desorption with any of these mordenites.

669

40 g

30 2010 ///,~\ ~ ~ ~ .k,/~~.~ 0

100

200

300

~-"

400

t

500

600

Temperature ! "C

Fig. 5(a) NO desorption during temperature programmed desorption (TPD) of NO observed with (--) CeNa-MOR(58), (- -) LaNa-MOR(57) or ("9 H-MOR. After pretreatmg a sample under argon f o r 5 - 6 h at 560 ~ NO adsorption was carried out at 100 ~ under NO (1024 ppm) flow at 100 ml/min for 2 -2.5 h, and consecutively, switched over to argon flow. After obtaming a stable zero signal, the temperature was raised at 5 ~ / mm.

2O

Cl U 0

8

lo 5 0 100

200

300

400

500

600

Temperature[ "C

Fig. 5(b) N20 desorption during the temperature programmed desorption (TPD) of NO observed with (--) CeNa-MOR(58), (--) LaNa-MOR(57) or (...) H-MOR. For experimental conditions, see legend in Fig. 5(a).

670 4. DISCUSSION

Cerium-exchanged mordenite and ZSM-5 showed a high NO reduction ability at 200 - 600 ~ which is actually the essential part of a real diesel exhaust temperature window (200 - 700 ~ This high activity of cerium-exchanged mordenite and ZSM-5 may be ascribed to its redox ability (Ce~/Ce rv) and to a strong oxidizing property of Ce rv [23]. Ce m ions are oxidized by oxygen to Ce rv, and Ce rv activates NO to NO2 (at 300 ~ or NO + (500~ efficiently promoting a finlher catalytic cycle. NO reduction selectivity towards nitrogen was considerably high over cerium catalysts. During our experiments, we have noticed that there was no N20 production over cerium catalysts for reactions in the presence of oxygen, such as NO reduction in the presence of oxygen and NO oxidation with 02 [23] N20 was observed during NO-TPD under an argon atmosphere. Over cerium-exchanged zeolite, the oxidation of NO towards NO2 (a NO-O2 reaction) [23] might be far more advantageous than the disproportionation of NO (a NO-NO reaction) towards N20 [31] in the presence of oxygen. However, tlfis does not nile out a possible N20 formation from a NH3-NO reaction [32]. Besides, it should be noted that ceritnu does not possess d-valence electrons. This may distinguish cerium from transition metals in its coordination behavior in catalysis. The exclusive selectivity towards nitrogen in the NH3 oxidation with oxygen is striking, considering the fact that NO or N20 production is observed with many other catalysts [13]. A reaction pathway of alrnuonia oxidation over cerium zeolite remains to be elucidated. The comparison of ammonia conversions in its oxidation and in the NO reduction illustrates a characteristic of flae NO reduction with ammonia over cerium zeolite. At lower temperatures, NH3 appears to be activated more easily under NO reduction conditions than with oxygen Olfly. This picture of reductant activation differs form that assumed for hydrocarbons, where the activation of hydrocarbons is regarded as an huportant factor for NO reduction [3, 27]. In a previous paper, we have proposed the intennediacy of NO2 in the NO reduction with ammonia at lower [23]. Tlfis hltennediate NO2 can probably oxidize temperatures (e.g. 300 ~ ammonia more efficiently than oxygen. At a higher temperature (> 400 ~ a~rnnonia oxidation with oxygen becomes substantial, and a certain reaction competition is expected between NO reduction and ammonia oxidation. The utilization of amlnonia for NO reduction was high (> 80 %) up to 500 ~ and starts declinhag at 600 ~ (Fig. 1). There are two other specific features observed in the catalysis of cerium zeolites. The first is the poor activity of CeNa-Y. A shuilar low activity of metalexchanged Y compared to ZSM-5 is reported h~ the NO decomposition with CuNaY [33], and in the NO reduction with methane over Co-Y [34]. Septilveda-Escribano

671 et al. have attributed this inferiority of Y to a lower stability of active copper species, i.e. Cu + [33], whereas Li et al. have suggested electronic influences from the specific

zeolite environment [34]. Other properties of zeolite Y can also be considered. The first is the presence of large cages and a high framework charge density, which allows the formation of CeOx clusters [29]. It should decrease the number of free coordination sites eventually leadhag to a low utilization of cerium ions. Such an oxide formation is more difficult to take place in a high silica zeolite as mordenite or ZSM-5, where cation sites are more remote from each other. Secondly, we mention the known preference of rare earth metal ions for positions in hexagonal prisms and sodalite cages [35] providing a low accessibility to reactants. The second specific feature is the high performance of partly H + exchanged cerium zeolites. As shown in Table 1, CeNaH-MOR and CeNaH-ZSM-5 exhibited higher activities than CeNa-MOR and CeNa-ZSM-5, respectively, in spite of a much lower cerium content. In addition, fully exchanged H-MOR becomes substantially active only above 300 ~ The activity of partly H+-exchanged cerium samples can not be explained by proportional contributions fi'om cerium and H § sites, indicating an ensemble effect of cerium and H + sites. It should be noted that H + sites were assumed to catalyze NO reduction through formation of NO2 as a reaction intermediate [36], while cerium was found to produce NO2 efficiently from NO and 02 [23]. Thus, H § sites perform probably more efficiently in cooperation with cerium sites, over which a large amotmt of intermediate NO2 is produced. NO-TPD results (Figs. 5(a) and 5(b)) hadicate a specific hateraction of NO with cerium-exchanged mordenite. First, the amotmt of NO desorbed from cerium is much higher than that observed on LaNa-MOR and H-MOR. NO desorption at around 290 ~ was particularly large with cerimn. The second feature is the reactivity of adsorbed NO on cerium. From LaNa- and H-MOR, NO was observed to desorb reversibly without substantial formation of N20, while NO was found to desorb as both NO and NzO from cerium mordenite. Since, N20 observed above 200 ~ is ascribed to a reaction of adsorbed NO [30], the high N20 formation up to the final temperature (560 ~ over cerium suggests a high reactivity of NO on the cerium zeolite surface. The large N20 peak at 300 ~ is apparently resulted from the disproportionation of NO, which orighmtes from the NO desorbed at 290 ~ With respect to this specifically high N20 fonnation over cerium, the redox couple (Cer"/Cerv) may be responsible according to: 2 N O + 2 Ce" + 2I-I+ --+ 2Ce rv + H20

+

N20

(1)

Although NO-TPD is informative on the specific interactions between NO and cerium, it probably does not fully reflect the behaviour of cerium under SCR conditions. In particular, the presence of oxygen may change the behaviour of these

672

species drastically, considering the observed shifted trend in catalysis in the presence of oxygen as discussed above. Further TPD studies using both NO and 02 may provide a more clear picture of the behaviour of these species under NO reduction conditions. In conclusion, the observed complete conversions of NFI3 and NO trader excess ammonia conditions (> 200 ~ indicates great potential of cerium zeolite. With ammonia applied in excess over NO, a stoichiometric amount of NH3 converts NO completely, and the excess NH3 will be simply converted to N2 by oxygen. With a certain shortage of NH3, a slightly lower NO conversion may be obtained, but ammonia will be exhausted in the NO reduction anyway. This flexibility in ammonia feed concentration makes an approximate reductant injection control applicable in practice. Under the present reaction conditions, an excess of ammonia up to 30 % is maximally allowed without ammonia slip. However, the effects of the reaction conditions, e.g., the space velocity, the presence of water or SO2, should be flirter examined to estimate such a "maximum ammonia excess value" in practice.

ACKNOWLEDGMENT

The authors would like to thank the Dutch Ministry of Housing and Environment (VROM) for their financial support.

REFERENCES

1

S. Sato, Y. Yu-u, H. Yahiro, N. Mizuno and M. Iwamoto,

AppL CataL 70 (1991) L1.

10 11 12 13

C.N. Montreuil and M. Shelef, AppL CataL B, 1 (1992) L 1. B.K. Cho, J. CataL, 142 (1993) 418. J.O. Petunclfi and W.K. Hall, AppL CataL B, 2 (1993) L17. K.C.C. Kaharas, H.J. Robota and D.J. Liu, AppL CataL B, 2 (1993) 225. G.P. Ansell, A.F. Diwell, S.F. Golunski, J.W. Hayes, R.R. Rajaram, T.J. Truex and A.P. Walker, AppL CataL B, 2 (1993) 81. E. Kikuchi, K. Yogo, S. Tanaka and M. Abe, Chem. Lett. (1991) 1063. M. Misono and K. Kondo, Chem. Lett. (1991) 1101. H. Hamada, Y. Kintaichi, M. Sasaki and T. Ito, Appl. CataL 70 (1991) L 15. K. Yogo, M. Ihara, I. Terasaki and E. Kikuclfl, Appl. CataL B, 2 (1993) L1, Y. Li and J.N. Armor, AppL CataL B, 2 (1993) 239. J.W. Byme, J.M. Chen and B.K. Speronell, Catalysis Today (1992) 33. H. Bosch and F.Janssen, Catalysis Today, 2 (1987) 436.

673 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36

U. Ozkan, Y. Cai, M.W. Kumthekar and L. Zhang, J. Catal., 142 (1993) 182. H.E. Cun3,-Hyde and A. Balker, Appl. Catal. A, 90 (1992) 183. W. Held, A. KOnig, T. Richter and L. Puppe, SAE 900496. F.G. Medros, J.W. Eldridge and J.R. Kittrell, Ind. Eng. Chem. Res. 28 (1989) 1171. S. Sato, Y. Yu-u, H. Yahiro, N. Mizuno and M. Iwamoto, Appl. Catal. 70 (1991) L 1. H. Yahiro, Y. Yu-u, H. Takeda, N. Mizuno and M. Iwamoto, Shokubai, 35 (1993)130. Y. Ukisu, S. Sato, A. Abe and K. Yoshida, Appl. Catal. B, 2 (1993) 147. H. Yasuda, T. Miyamoto, C. Yokoyama and M. Misono, ShokubaJ, 35 (1993) 386. C.M. van den Bleek and A.W. Wypkema, The D.U.T. NOx/Urea Process phase 3, NOVEM report contractnr. 42.33-005.30 (1990). E. Ito, R.J. Hultermans, P.M. Lugt, M.H.W. Burgers, M.S. Rigutto, H. van Bekkum and C.M. van den Bleek, Appl. Catal. B, (1994) in press. E. Ito, C.M. van den Bleek, H. van Bekkum, J.C. Jansen, R.J. Hultermans and P.M. Lugt, Deltt Universityof Tedmology, Dutch Patent Appl., NL 93.02288 (1993). R.J. Hultennans, E. Ito,/i,. J6zsef, P.M. Lugt and C.M. van den Bleek, in the present proceedings of the third international sympositun of Catalysis and Automotive Pollution Control III (CAPoC3), Brussels, April 20 - 22, 1994. E. Ito, R.J. Hultermans, P.M. Lugt, M.H.W. Burgers, H. van Bekkum and C.M. van den Bleek, paper in preparation. J.L. d'Itri and W.M.H. Sachtler, Catal. Lett., 15 (1992) 289. W. Kladhlg, dr. Phys. Chem., 80 (1978) 262. E.F.T Lee and L.V.C. Rees, Zeolites, 7 (1987) 446. Y. Li and J.N. Armor, Appl. Catal., 76 (1991) L1. M. Niwa, Y. Fun~awa and Y. Murakami, J. Coll. Int. Sr 86 (1982) 260. L. Singoredjo, R. Korver, F. Kapteijn and J. Moulijn, Appl. Catal. B, 1 (1992) 297. A. Sepfilveda-Escribano, C. Mfirquez-Alvarez, I. Rodoigez-Ramos, A. Guerrero-Ruiz mid J.L.G.Fierro, Catalysis Today, 17 (1993) 167. Y. Li and J.N. Annor, Appl. Catal. B, 2 (1993) 239. W.J. Mortier (Editor), "Compilation of extraframework sites in zeolite", Butterworth Scientific Limited, London. P.M. Hirsch, Environmental Progress, 1 (1982) 24.



675

SELECTIVE REDUCTION OF NO OVER COPPERCONTAINING MODIFIED Z E O L I T E S J. Hal~isz, J. V a r g a , G. S c h 0 b e l , I. Kiricsi, K. H e r m i d i , I. H a n n u s , K. V a r g a , a n d P. F e j e s

Applied Chemistry Department, J6zsef Attila University Rerrich tdr 1, H-6720 Szeged, Hungary ABSTRACT

The most efficient method for NO removal from stationary and mobile sources is catalytic reduction with ammonia, hydrocarbons, CO or H2. Modified zeolites are active catalysts in these processes. For Cu-ZSM-5 especially high activity and stability have been reported. In this work the properties of copper-containing ZSM-5 zeolites prepared by wet or solid state ionexchange have been investigated. The Br6nsted acidity of the Cu2+-exehanged samples was much lower than that of the parent zeolites, and they had high activity in selective reduction with ammonia, propene or propane. A comparison of Cu-ZSM-5 activity in the decomposition of NO and in the reaction of NO with propene or propane revealed that the hydrocarbons as well as the nitrogen oxides play important role in the performance of NO reduction catalysis.


The removal of nitrogen oxides from combustion and industrial exhaust remains an important problem which has been studied extensively. Combustional modifications (controlling burner stoichiometry and lowering flame temperature) have led to methods that are both cost-effective and energy-efficient, however, these methods by themselves cannot achieve the reduction of NO, to levels required in new regulations [1 ]. The wet methods (and the adsorption techniques) for NOx control, which can be used for stationary source emissions only, are expensive to operate and additionally, these methods have serious problems with adsorbent treatment and disposal [2].

676 Selective non catalytic reduction (SNCR) with NH3 is limited to industrial boilers in consequence of the relatively narrow temperature range for the reaction. Selective catalytic reduction (SCR) by ammonia has high efficiency and it can be used for many stationary sources, especially for nitric acid plants [1], and it is based on the catalytic pairing of nitrogen atoms, one from nitric oxide, one from ammonia. This method, however, is unsuitable for small sources and vehicles. As far as automotive emission is concerned nonselective catalytic reduction (NSCR) by hydrocarbons, CO and 1-12from the exhaust stream has been reported over various catalysts recently [1,3,4]. The discovery by Iwamoto et al. in 1981 that copper-exchanged zeolite Y possesses high and stable activity for the direct decomposition of NO was the breakthrough which strongly suggested that a practical NO decomposition catalyst could be developed on zeolite basis [5]. It has been shown that catalysts based on copper-exchanged ZSM-5 are also very active for direct decomposition and selective reduction is also feasible with hydrocarbons, especially with propene [6]. The activity of copper-exchanged zeolite catalysts in direct decomposition was influenced by (i) the degree of copper ion-exchange [7] (no decomposition was observed in the absence of copper) and (ii) the Si/A1 ratio of the zeolite [8], (iii) the preparation method of the parent Na-ZSM-5 [9]. The effect of admixed dioxygen and water vapour to the feed stream has been reported too [10]. For catalytic reduction processes, in which hydrocarbons were used as reducing agents, copper exchanged zeolites showed the best performance, for example for propene containing feed compositions [ 11 ], since close to 100% NO conversion could be attained at as low as 623 K. An acidic form of iron-silicate showed high activity and stability for reduction of NO with propene, but this catalyst was very sensitive to the presence of SO2 in the feed [12]. Metallosilicates having ZSM-5 structure [13,14] seem to be a new class of catalysts for these reactions. The objective of present paper has been to study the role of Cu-containing modified ZSM-5 type zeolites in the reactions of nitrogen monoxide. 2. EXPERIMENTAL

Nitric oxide decomposition and reduction by ammonia, propene or propane were carried out on H-ZSM-5, Cu 2+ion-exchanged X-type and ZSM-5 zeolites.

677

2.1. Catalysts The Na-form of zeolites were synthesized by usual methods. Modification of ZSM-5 zeolites was carried out by two different methods: (i) conventional ion exchange in Cu2+-acetate solution, and (ii) heat treatment of the physical mixtures of CuC12 and H-forms of zeolites at 873 K (solid-state ion exchange). In liquid phase the copper-ion exchange was carried out by stirring about 25 g sample in 0.05 M Cu-acetate solution at room temperature for 24 hours, the exchanged sample was washed, dried and calcined at 773 K for 5 hours. The solid-state ion-exchange was carried out by baking the physical mixture of H-ZSM-5 and CuCI2 at 873 K for 6 hours. 2.2. Catalyst characterization Composition of samples and copper ion-exchange level were determined by X-ray fluorescence (XRF) analysis. The catalysts were characterized by X-ray diffraetometry (XRD) and infrared (IR) spectroscopy. Acidity of the catalysts was tested by pyridine adsorption monitored by IR spectroscopy. Self-supported wafers pressed from zeolite powder (thickness 15 mg cm2) were placed in the sample holder and outgassed at 770 K in vacuum (final vacuum was better than 103 Pa) for 2 hours followed by cooling to room temperature where the specman of the activated zeolites were registered. 1.33 kPa pyridine was adsorbed at 473 K for 1 hour followed by evacuation at the same temperature for 1 h. For calculating the concentration of acid sites extinction coefficients available in the literature were used [15].

t r a n s m i t t a

A B

n c e

I

1200

Fig.1.1R-~

I

|000

I

800

I

600

....

~Icm

-!

of H-Z_q~-5 (A) Cu-Zsm-5/con .(B) ~

C u ~ - 5 / s o l . ('C)

678 2.3. Reaction studies The NO reactions (decomposition and reaction with propene or propane) were carried out in a recirculatory batch reactor with mass spectrometric analysis (details see in [2]). The catalyst sample (0.5 g) was activated in dioxygen at 723 K for 4 hours before each measurement. The gas-phase concentrations of reactants and products were measured by mass spectrometry. Mass numbers 41 of propene, 43 of propane, 46 of nitrogen dioxide and 30 of NO were used for analysis. The SCR reaction (with NH3) was studied in a fixed-bed flow reactor with gas chromatographic (GC) analysis. The inlet gas composition was 10% NO + 10% Nil3 in nitrogen; the feed rate was 120 cm3/min (GHSV = 1500) at atmospheric pressure. Before each run, 5 g of the catalyst was pretreated in flowing air at 773 K for 2 h in tubular quartz reactor. Reactant and product analysis was performed by thermal conductivity detector using Porapack-Q colulma.

3. RESULTS AND DISCUSSION 3.1. CATALYST CHARACTERIZATION Table 1 shows the Si/A1 ratio, Cu content and the acidities of catalysts used.

Table 1. Properties of catalysts used Si/A1 ratio

Sample

CuZSMSJcon

Ell content mass %

Acidity/ktmol g-~

Br~3nsted

Lewis

,,

138

23

021

0.588

Cu-ZSM-5/sol. ]l

14.5

2.7

0.027

0.289

3.1.1. Characterization by IR spectroscopy Catalysts prepared were characterized by IR spectroscopy using the KBr matrix method generally applied to check the changes in the framework vibration region (400-1300 cm-1). As it can be seen in Fig. 1, non of the conventional exchange method (B) and of the solid state exchange (C) resulted in observable structural changes.

679

3.1.2. Characterization by XRD Each modified catalyst sample preserved the crystal structure characteristic of zeolite ZSM-5. No reflexions due to separate copper oxide phases could be detected for the solid-state exchanged material. 3.1.3. Acidity measurements Upon adsorption of pyridine IR bands at 1540 and 1450 c m "1 appear characteristic for BrOnsted and Lewis acid sites, respectively. The band at 1490 cm-~ is due to the combination vibration of both types of acid sites. On pyridine adsorption the OH band typical of BrOnsted acidic hydroxyl groups disappeared while those of the terminal SiOH groups only decreased in intensity (see Fig. 2). These observations reflect the different acidity of these OH groups. The parent Na-ZSM-5 sample possessed no BrOnsted acidity detectable by this method. 3.2. Catalytic measurements Selective reduction of NO was investigated in the absence and presence of propene, propane or ammonia.

C

1600

1500

u

-

Z

S

M

-

5

/

c

o

400 1300

n

C u-ZS M-5/sol.

.

Cm ~

1600

1500

1400

1300

cm

-1

Fig.2. Determmation of acidity of Cu-ZSM-5 by pyridine adsorption

680

concentration/%

loi -~ [" o ~

rn

~

o o

o

~

_

_

o..

o _ a b l- i

NOx in NH3 in NH3 NOx

out out

time on stream/hour

Fig.3. Selective reduction o f NO over Cu-ZSM-5 zeolite at 573 K in fixed bed flow reactor.

3.2.1. Selective reduction with ammonia In the selective reduction of NO with ammonia the Cu-ZSM-5 prepared by conventional ion exchange proved to be an effective catalyst, as can be seen in Fig. 3, where the results of reaction at 573 K is presented. The NO conversion to N2 was higher than 95% throughout the run. In case of H-ZSM-5 only 15% conversion for NO and 12% for NH3 was observed due to the high Br6nsted acidity of this catalyst. The activity of Cu-X zeolite was much lower than that of Cu-ZSM-5 at the same temperature (57% conversion for NO and 60% conversion for ammonia). 3.2.2. NO decomposition In the absence of any reducing agent NO over Cu-ZSM-5 prepared by wet method transformed to N2 and NO2 with molar ratio of 1:2 in a closed recirculatory reactor system (Fig. 4). This transformation has taken place with measurable rate above 573 K. 3.2.3. Catalytic reduction with propene In the reduction proceeding in the presence of propene, formation of N2, H20 and COz was detected over the copper containing catalyst. Kinetic curves of NO consumption (Fig. 5) showed that the reaction was very slow at 473 K, fast at 593 K and above. The propene consumption (adsorption) was so fast that its disappearance could not be followed under these experimental conditions. The measured kinetic curves are depicted in Fig 6.

681 relative intensity

100 ~ . ~ NO

75-

50NO 2

25-

-- N n 2

A w

I

I

10

I

I

20

30

4O tL~e/min

Fig. 4. Decompositionof NO over Cu-ZSM-5 at 623K

NOn.ion CA) 103

T=593 K T=573 K ~

....1r

r

T=530K

20 I

40

I

80

I

120

I

160

i

2OO

I

240

firr~rrin

Fig.5. Temperature dependence of NO transformaton over Cu-ZSM-5/con. in the presence of propene.

682 Relative intensity lOO NO N2

50

|

lO

i

20

30

!

|

40

50

!

time/min

Fig.6. Kinetic curves of NO transformation over Cu-ZSM-5/con. in the presence o f propene.

3.2.4. Catalytic reduction with propane As Fig 7. shows completely different temperature range was required for NO reduction with propane. Here, the consumption of NO was easily measurable even at 823 K. The kinetic curves reveal that below 673 K only very slow reduction occurred. As far as the transformation of hydrocarbons is concerned, complete consumption was observed for propene over 600 K, but it was not the case for propane. Fig 8. shows the kinetic curves measured for a typical reaction parameter set. The NO conversion over Cu-ZSM-5 prepared by solid-state ion-exchange was much slower than that of over catalyst prepared by conventional method (comparable activity was detected at the temperature of 100 K higher); this behaviour could be attributed to the very low Br0nsted acidity of this sample.

683

NO conversion (%) 100

~

~

723 K

50

673~= 623 K

|

i

10

i

20

i

30

i

i

40 50 time/min

60

Fig.7. Temperature dependence of NO transformation over Cu-ZSM-5/con. catalyst in the presence of propane

Relative intensity 100

N2

Propane

50

NO I

10

i

20

I

30

i

40

I

50

60

i

time/min

Fig. 8. Kinetic curves of NO transformation over CU-ZSM-5/con. in the presence of propane.

684 4. CONCLUSIONS

(i) copper containing ZSM-5 zeolite catalysts are capable of NOx conversion up to 90% at temperatures over 670 K; (ii) both ammonia and C3 hydrocarbons are effective agents in the NO~ reduction, however, the catalyst made by wet ion-exchange method is more active in the reactions with propene or propane than that of the sample prepared by solid exchange; (iii) the role of BrOnsted acidic sites is to promote the formation of carbonaceous deposits which can be act as active centres in this process [16]; (iv) the effect of oxygen addition was dependent on the method of ion-exchange and the O2/NO pressure ratio. ACKNOWLEDGEMENT

The financial support of the National Science Foundation of Hungary (OTKA No. T 007601 and 1182/90) is gratefully acknowledged. REFERENCES

H. Bosch and F. Janssen, Catal. Today, 2, (1988) 369. I. Hannus, J. Halfisz, I. Kiriesi, Gy. SehObel, Gy. Tasi and P. Fejes, Acta Phys. et Chem. (Szeged) 35, (1989) 3. G. Centi, S. Perathoner, Y. Shioya and M. Anpo, Res. Chem. Intermed., 17, (1992) 125. M. Iwamoto, in "Future Opporttmities in Catalytic and Separation Technology, Stud. Surf.-Sei. Catal., 54, (1990) 121. M. Iwamoto, H. Fund~awa and S. Kagawa, Stud. Surf. Sei. Catal., 27, (1986) 943. M. Iwamoto, H. Hamada, Catal. Today, 10, (1991) 57. M. Iwamoto, S. Yokoo, K. Saaki, S. Kagawa, JCS Faraday Trans.I., 77, (1981) 1629. M. Iwamoto, H. Yahiro, Y. Mine, S. Kagawa, Chem. Lett., (1989) 213. 7 Y. Li, J. N. Armor, Appl. Catal., 76, (1991) L 1. 8 V. P. Shirakar, A. Clearfield, Zeolites, 9, (1989) 363. 9 10 M. Iwamoto, H. Yahiro, K. Tanda, Stud. Surf.-Sci. Catal., 44, (1989) 219.

685 11 12 13 14 15 16

B. K. Cho, J. Catal., 142, (1993) 418. E. Kikuchi, K. Yogo, S. Tanaka, M. Abe, Chem. Lett., (1991) 1063. K. Yogo, M. Ihara, I. Terasaki and E. Kikuchi, Appl. Catal. B2, (1993) L1. K. Yogo, M. Ihara, I. Terasaki and E. Kikuchi, Catal. Lett., 17, (1993) 303. J. Datka, J., Catal., 102, (1986) 43. G.P. Ansell, A.F. Diwell, S.E. Goltmski, J.W. Hayes, R.R. Rajaram, T.J. Truex and A.P. Walker, Appl. Catal. B2 (1993) 81.



687

Z E O L I T E C A T A L Y S T F O R T H E PURIFICATION OF AUTOMOTIVE EXHAUST GASES

Delia Florea, Lucia Georgescu, Floreta Constantinescu, D u m i t r u M~noiu, Dinu Gaber, Mihaela C o m ~ e s c u . Research Institute f o r Petroleum Processing and Petrochemistry-ICERPPloiesti. B-dul Republicii no. 291 A - Romania

INTRODUCTION

The latest literature data include a new catalytic process for nitrogen oxides (NOx) selective reduction with hydrocarbons in oxidizing atmosphere on heterogeneous catalysts such as alumina [1], H - form zeolites [2] and metal supported zeolites [3, 4]. This process breaks the widely accepted concept that ammonia is the only selective reductant for NOx in the presence of oxygen and the hydrocarbons are not useful for the selective reduction. The new process of selective reduction is remarkably improved in the presence of oxygen or even SO2 and can be used for the purification of exhaust gases from engines (Diesel or gasoline type). Generally, copper modified ZSM - 5 zeolite (Cu-ZSM-5) has been reported to have a high activity in reduction of nitrogen oxides (NOx) by hydrocarbons under net oxidizing conditions. Recently, gallium ion exchanged ZSM-5 catalyst showed extremely high selectivity for the reduction of nitric oxide by ethene in the presence of excess oxygen [5]. Based on the above mentioned data the paper shows the results of research performed for a Cu-ZSM-5 catalyst production to the purpose of purification of vehicle engines exhaust gases. The influence of the ion exchange level in ZSM-5 upon the catalytic performances is also studied. The catalysts used were CuZSM-5 granules or Cu-ZSM-5 coating on a ceramic monolith. The trials of correlation between the catalysts performances and the state of copper in catalysts prepared is also showed.

688 EXPERIMENTAL

Na-ZSM-5 having a molar SiO2 / A120 3 ratio of 42 was supplied by the factory of catalyst Vega. Copper ion exchanged ZSM-5 was prepared by the ion exchange of ammonium form ZSM-5 using an aqucous solution of copper acetate 0,06 M. Copper ion exchanged ZSM-5 catalysts with an excess loading of copper ions were prepared according to the method reported by Ywamoto et al [6]. The catalysts were produced by binding the Cu-ZSM-5 with alumina and nitric acid 10% and their formation as granules. Than, the catalysts were dried at 120~ and calcinated at 500~ The amount of copper in zeolite was determined by atomic absorption spectroscopy. The catalysts test samples having a cylindrical ceramic monolithic substrate (258 cells/in2, 35 mm in diameter x 120 mm in length) were also produced. To prepare the catalysts, a cylindrical ceramic monolithic substrate was coated with a washcoat consisting of zeolite (69%) and silica (31%). The ZSM-5 had a silica alumina ratio 43,5. The copper ions were introduced in ZSM-5 by ion exchange with an aqueous solution of copper acetate - 0.06M. The ion exchange was performed after the coating of the monolithic substrate. The amount of zeolite on the monolithic substrate was 16-19%, and the copper content in the samples was 0.4 - 0.6 % corresponding to an exchange level of copper (> 100%). As a reference, a monolithic oxidic catalyst type CuxCo3_xO 4 (x=l) was prepared by coating the monolithic substrate with a washcoat consisting of alumina and cobalt - copper oxides. The cobalt and copper content in this catalyst was 33 g/l - Co and 18 g/1 - Cu, corresponding to 4.2% metal content in catalyst. The performances of the catalyst prepared were estimated by model reaction tests which consist in NOx (NO + NO2) reaction with methane and methane oxidation, performed in a laboratory test unit coupled with gas cromatografs. 3.5 g of the catalyst crushed in 1-1.6 mm was packed in a stainless steel tube of 16 mm inner diameter. The desired reaction gases were prepared by means of the mixing gas pumps type 4 WOsthof OHG - Bochum (Germany). The gases were routed through a by-pass line for analysis and finally routed through the catalyst. The reactant mixture contained 0.16 % NO2, 1% methane and 20% oxygen in nitrogen with a total flow rate of 1630 cm3/min. (w/F = 0.13 g 9s 9cm -3) in the test of NO2 reduction with methane, and 1.5% CH4 in air with a total flow rate of 830 cm3/min. (w/F = 0.25 g. s. cm -3) for test of methane oxidation. The effluent reactor was analyzed by gas chromatografs equipped with a molecular sieve 5A column (for nitrogen and carbon monoxide) and a Porapak Q column (for nitric oxides, carbon dioxide and methane). The formation of nitrous oxide was hardly detected and the activity of the selective reduction was evaluated in terms of the conversion of nitric oxide to nitrogen.

689 The activity of the catalysts samples having a cylindrical monolithic substrate were determined only in the model reaction test of methane oxidation, performed in a laboratory test unit coupled with gas cromatografs, equipped with a special reactor for testing monolithic samples. The state of copper in the prepared catalysts was studied by ESR spectroscopic technique and by thermal analysis in flow hydrogen medium. Experimental measurements were performed with a spectrometer ART-6 in X frequency bands analysis (u = 9010 MHz) and a thermoanalitical instrument SETARAM. RESULTS

AND DISCUSSION

In fig.1 is presented conversion of nitric oxides and methane versus concentration of oxygen. From the above figure is possible to see that nitric oxides conversion remain practically unchanged at a increasing of oxygen amount from 4% to 20%. The methane conversion have a increase at increasing of oxygen concentration. At a concentration of 20% oxygen the conversion of methane reaches 100%. Taking in consideration these experimental dates our work was carried out at a 20% oxygen concentration with the purpose to see how is the evolution of NOx conversion in case when hydrocarbons from reaction mixture are converted just before nitric oxides consumption.

90 80

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.

.

.

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.

C o n y NOx to N2 (%) C o n v G H 4 (%)

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I

I

I

l

I

I

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6

8

10

12

14

16

18

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Fig. 1. Effect of oxygen concentration on the reduction of NOx with methane and the methane oxidation over Cu-ZSM-5 (126) at 450~ (Reaction conditions: NOx: 0.16%, CH4: 1%, w/F=O.13g.s.cm-3)

690 Table 1 shows activity of catalysts obtained from ZSM-5 zeolite modified with copper at which the ion exchange level of the copper varied from 55% to 126% in the reduction reaction of NOx with methane. The catalysts with a 100126% degree of ion exchange of the copper have been found to show a higher conversion of the nitrogen oxide to nitrogen, especially at lower temperatures (300-400~ The activity of zeolite type catalysts is compared with the activity of an oxide catalyst supported on alumina, type CuxCo3_xO4 where x=l. Although the literature data report a good activity in the selective reduction reaction of nitrogen monoxide with propane [7] for a number of Cu/A120 3 and Co/A120 3 catalysts (especially for those prepared from acetates and calcinated at temperatures of 600~ or higher) and for alumina itself, the catalyst CuxCo3_xO4 with 8% cobalt and 4% copper has no activity in the reduction reaction of nitrogen monoxide with methane. We mention that this catalyst was prepared from cobalt and copper nitrates and calcined at 500~ Table 1 also includes methane total conversion in the reduction reaction of NOx with methane and selectivity to carbon dioxide. The ability of Cu-ZSM-5 catalyst~ifor hydrocarbon oxidation is generally known. Watchind the data presented in table 1, the activity of zeolite type catalyst in methane oxidation reaction is found to be comparable with the activity of the oxide catalyst even higher for the catalysts resulted from zeolite in which the copper degree of ion exchange is 124-126%. Such catalyst start converting the methane (as well as NOx) at lower temperatures (300-400~ A high selectivity for methane oxidation ca be remarked for all the tested catalysts. At the temperature of 500~ methane conversion reaches values of 100% while NOx conversion to nitrogen reaches values of only 50-60% for most tested catalysts. However NOx conversion rapidly increase to 100%, within a narrow temperature range (500550~ after methane conversion reached 100%. Such behaviour could give us certain indications upon the reaction mechanism. From among the reaction schemes which have been proposed for the conversion of NO x to nitrogen in the presence of hydrocarbons and oxygen excess, the one that suggest the coke deposited on catalyst surface as an active intermediate in NOx reduction reaction, seems to be supported by our results [8]. Although the methane oxidized entirely, the deposits existing on catalyst surface play a reducing role and reduce NOx to nitrogen when this reaction is no more in competition with methane oxidation reaction. Zeolite catalyst performances were also checked in a direct manner in the methane oxidation reaction, a model reaction which tested the spinel oxide type catalysts prepared by us for hydrocarbons oxidation to the purpose of purifying engines exhaust gases. The results are presented in Table 2. From among the

Table I. Red~rcliorzof rzitric oxides (Nod over granular catalysts w/F Reaction conditions: NO, - 0.16%, CHq - I %, 0 2 - 20%

Catalyst

Metal content

=

0.13 g . s . ~ r n - ~

Conversion of NO, to N2 (%)

(YO)

3OO0C 400°C 500°C 550°C 2 100 100 C U,.~ C O,. ?-~OA 8-Co,4-Cu Cu - ZSM - 5 (55) 0.84 - Cu 47 100 11 100 100 1.856 - CU 63 100 63 100 CU- ZSM - 5 (108) 28 38 61 100 11 20 100 100 Cu - Z S M - 5 (126) 1.9 - Cu 2.3 - CU 26 57 100 9 26 100 100 CU- ZSM - 5 (124) Values in parentheses for the expression of the catalysts represent the level of cation exchange. (%)

a

300°C 400°C 5OO0C 550°C

Conversion of CH4

Selectivity to C 0 -2

(YO)

300°C 4OO0C 500°C 550°C 11 88 93 8 77 93 22 97 100 2 15 85 97 18 80 85

692 zeolite type catalysts, those whose copper degree of exchange in zeolite is > 100% achieve higher methane conversions. Such results are in agreement with those obtained in the reduction reaction of nitrogen monoxide with methane and confirm the fact that those catalysts with high activity on NOx conversion to nitrogen have also a high activity on methane oxidation. Table 2. Catalytic activities o f granules catalysts m reaction o f methane oxidation. Reaction conditions: C H - 1.5%, 0 2 - 20% in N 2 w/F = 0.25 g . s . cm -3

Catalyst CuxCo3_xO4 (8% Co, 4% Cu) Cu-ZSM-5 (55) Cu-ZSM-5 (108) Cu-ZSM-5 (126) Cu-ZSM-5 (124)

Conversion of CH4 (%) 400~ 500~ 10 52 11 42 15 43 14 57 16 55

..

Selectivity to CO2 (%) 400~ 500~ 13 53 5 29 6 43 9 56 9 66

The ESR studies performed on the catalysts whose activity data are here in above presented show the existence of copper absorbed in the lattice under two forms which according to the literature data would be Cu 2+ and Cu +. The samples of Cu-ZSM-5 (126) and Cu-ZSM-5 (124) show higher absorbed spins into the lattice as Cu-ZSM (55) sample. These results are in good agreement with the higher catalytic activity of these samples. Reduction in the flow system with hydrogen at different temperatures (from room temperature to 900~ give a significant difference between the samples. Fig. 2 shows that for the Cu-ZSM-5 (55) sample with an ion exchange level under 100%, the reduction of copper occur in a single step at a higher temperature (810~ This fact demonstrated that at a lower copper content, this exists in a single form according to this method. For the samples with higher copper content the reduction of this cation occur in two steps. The first step takes place between 520~ and 605~ with a maximum at 565~ the second step was found between 760 and 960~ with a pick at 845~ An exploration of this fact might be that copper exists in two forms, in good agreement with the published literature which shows that for the zeolites with large amounts of copper, this cation exists as Cu 2+ and Cu +. The ESR spectra for reduced samples with hydrogen have a different aspect. In the case of Cu-ZSM-5 (124) and Cu-ZSM-5 (126) the signal is lower than the signal of Cu-ZSM-5 (55) sample. This fact shows a large amount of copper which is possible to be reduced in the samples with the higher copper content. If the

693

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-bFig. 2 TGA / DTA curves of: a-CuZSM-5 (124) b-CuZSM-5 (55) reduced samples remain in air for a few hours spin number increases but below toinitial value. A redox cycle Cu 0 r Cu + r Cu 2+ in zeolite, quated by the literature data [9] could justify such modification. The results obtained with granulated catalyst were checked with monolithic catalyst. The samples with a copper content of 0.6 wt % and 0.4 wt %, with an exchange level of copper over 100% and with nearly the same amount of zeolite

694 deposited on the monolithic substrate (16-19wt%) were tested in the oxidation reaction of methane. Fig. 3 shows the catalytic activity of monolithic samples in the oxidation reaction of methane in comparison with the catalytic activity of the oxidic type sample CuxCo3_xO 4 (4.2) (x=l). This latter sample is a representative catalyst for hydrocarbons oxidation. Zeolite catalysts samples show a lower activity than the oxidic catalyst, but the Cu-ZSM-5 sample with the copper content of 0.6 wt % approaches this catalyst. The plot of reaction selectivity to carbon dioxide versus temperature is presented in fig. 4 and shows the same behaviour as that of the studies samples. CuxCo3-x04(4.2) - 4 - C u Z S M - 5 with copper content 0.6 wt % "- CuZSM-5 with copper content 0.4 wt %

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Fig. 3 Variation in the convertion o f methane as a function o f reaction temperature. (Reaction conditions: O.4% CH 4, 20% 02 in N 2 Sample volum - 147 cm 3, space velocity- 10000 h -1)

In the case of monolithic catalysts, the ESR spectra present the same aspect as the granular samples. The copper is absorbed in the lattice under two forms which according to the literatura data would be Cu 2+ and Cu +. The number of spins is larger in the case of Cu-ZSM-5 sample with the copper content of 0.6 wt % than in the case of Cu-ZSM-5 with the copper content of 0.4 wt %. This fact is

695 also in good agreement with the catalytic activity, in a similar maner as in the case of granular catalysts. The reduction study with hydrogen of the monolithic catalysts under the same reduction conditions as for granular samples shows that in this case there is only a single reduction step at high temperature (910~ After reduction a specific ESR signal appears for copper only in the Cu-ZSM-5 sample with the copper content of 0.6 wt %. This fact indicates that the amount of unreducible copper is large in this catalyst.

-~-Cux

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According to the literature it is very important to have copper too in the catalyst, which is difficult to reduce in order to carry out NOx reduction with hydrocarbons in the presence of oxygen.

696

CONCLUSION The results presented in this paper have confirmed the fact that the zeolite type catalysts which are highly active in methane oxidation reaction, are also highly active in NOx reduction reaction. They also have tried to explain copper state in the zeolite type catalysts used in the reduction reaction of NOx with hydrocarbons in the presence of a greater amount of oxygen in the reaction medium, therefore under distinctly oxidizing conditions. They evidenced the importance of copper excess in such catalysts (the level of copper ion exchange in ZSM-5 over 100%) and confirmed the literature data which show that copper is present on the surface of these catalysts under two forms (Cu2+, Cu+) [6, 9]. Catalysts behaviour in the reduction reaction of NOx with methane under distinctly oxidizing conditions supports the literature data showing that the reducing agent for NOx could be represented by certain species deposited on catalyst surface (probably coke) which make possible NOx reduction even alter the complete oxidation of the methane from the reaction medium [8].

REFERENCES Y. Kintaichi, H. Hamada, M. Tabata, M. Sasaki and T. Ito, fatal. Lea., 6 (1990) 239. H. Hamada, Y. Kintaichi, M. Sasaki, T. Ito and M. Tabata, Appl. fatal. 64 (1990) L. S. Sato, Y. Yu-u, H. Yahiro, N. Mizuno and M. Iwamoto, Appl. fatal. 70 (1991) L. M. Iwamoto and H. Hamada, Catalysis Today 10, 57-71-(1991). K. Yogo, M. Ihara, I. Terasaki and E. Kikuki Appl. fatal.- B. Environmental, 2 (1993) L 1 - L 5. M. Iwamoto, H Iahiro, S. Shundo, Y. Yu-u and N. Mizuno, Appl. fatal. 69 (1991) L15 - L19. H. Hamata, Y. Kintaichi, M. Sasaki and T. Ito., Appl. fatal. 75 (1991) L 1 - L8. G. P. Ansell, A.F. Diwell, S. E. Golunski, Y. W. Hayes, R. R. Rajaram, T. J. Truex and A. P. Walker, Appl. fatal. B, Environmental,2 (1993) 81 - 100. R. Burch and P. J. Millington, Appl. fatal. - B Environmental, 2 (1993) 101 - 116.

A. Frelmet and J.-M. Bastin (Eds.) Catalysis atld Automotive Pollution Control III Studies in Surface Science and Catalysis, Vol. 96 1995 Elsevier Science B.V.

697

S T U D I E S O F S E L E C T I V E N O R E D U C T I O N B Y CH4 A N D CH3OH OVER Co AND Cu EXCHANGED MORDENITE

J. Vassallo, M. L e z c a n o , E. M i r 6 and J. P e t u n c h i Instituto de I n v e s t i g a c i o n e s en Catdlisis y P e t r o q u i m i c a - I N C A P E (UNL, F I Q - C O N I C E T ) - S a n t i a g o del E s t e r o 2 8 2 9 - 3 0 0 0 - S a n t a Fe, A r g e n t i n a

ABSTRACT

A systematic study of the selective reduction of NO using CH4 and CH3OH as reducing agents is presented. CoMordenite proved to be active and selective for both reactants while CuMordenite was so only when CH3OH was used. The redox properties of the solids could explain that behavior. Interestingly, the NO to N2 conversion started alter the CH3OH conversion reached 100%. Experiments made without oxygen in the feed stream showed a strong deactivation of the catalysts when methanol was the reducing agent, probably due to carbon deposits on the solid surface. The same effect was observed by transient experiments when oxygen was removed. Results showed that CH3OH could be an oxygenated intermediate on the selective reduction of NOx with CH4 over CoMordenite.


More efficient engine performance can be achieved by ushlg higher air-fuel ratios than those perlnitted by the "whldow" required for present three-way catalyts [1]. Thus, the development of a suitable NOx reduction catalyst would be highly desirable. Earlier reports on the use of hydrocarbons as selective reducing agents for NO in the presence of excess oxygen [2,3] have led to an hacreasing interest in these reactions because of their obvious practical importance. Although the general characteristics of these reactions are by now well known, flae reaction mechanism is not completely tmderstood and several suggestions have been advanced. A redox lnechalfism has been proposed by Burch and Millfiagton [4], while other authors have related active sites with the fonnation of carbon residues [5]. The possibility of a biftmctional redox-acid mechanism has been reported ha [6] as well as

698 the preferential NO reaction with O~ to fonn NOz as the haitial stage of the reaction [7]. However, one of the suggestions which have deserved more attention proposes the existence of an oxygenated hatennediate, which would be responsible for NO reduction [8]. In the present work, tiffs topic is further investigated through a systematic study of flae selective reduction of NO by CI-L and CH3OH over metal zeolites. Accordingly, file role of file partial oxidation hydrocarbon in flae reaction mechanism of the selective NO reduction is considered.

2. EXPERIMENTAL The catalysts employed, Cu and Co Mordenite (herehlatter CuM and CoM) were prepared by iolfiC exchange of a LZM5 Mordenite provided by Linde (Si/A1 5.0 ratio), and aqueous solutions of CttAc (0.012 M) and CoNO3 (0.025 M). The exchange was perforlned at ambient telnperature, using Mordenite/solution ratios of 1 g/It mid 3 g/lt, respectively. In all cases, the preparation was perforlned during 24 hours m~d pH = 5. The solids obtah~ed by filtration were dried on a stove at 120~ and afterwards calcined hi Oz at 500~ The alnotmt of exchanged metal was detennined by atomic absorption, 54.5% of the C.E.C. (cation exchange capacity) corresponding to CuM, and 25.0% to CoM (5.9 wt% and 2.4 wt%, respectively). The kinetic experiences were carried out ha a quartz tubular reactor (1.3 cm o.d. and 50 cm in length) trader steady state conditions. The feed composed of He, NO and HC (whether CH4 or CH3OH) was introduced to the reactor alter mi~ag in a manifold. 02 was hlcorporated to the gaseous mixture close to the catalytic bed (about 2 cm above tiffs one) with the purpose of milmnizing reactions ha flae gas phase, especially when CH3OH was used as reduchlg gas. ha order to study the reaction CH3OH+NO+O2 ha the gas phase, experiments were performed replacing the catalyst bed by the same voltune of quartz chips. ha all experiences the composition of the feed consisted ha NO (1000 ppm), CH4 or CH3OH (1000 ppm), O2 (1%) and He as diluthag gas. CH3OH was introduced to the manifold by means of a saturator at 0~ The total stream employed was 150 cm3/min mad the catalyst load was 0.5 g hi every case (GHSV 6500h1). The gaseous effluents were analyzed by gas chromatography (SHIMADZU GC-8A) employing a 5A zeolite to separate N2, 02, NO, C O , CH4, and chromosorb to separate CO2, CH3OH and N20. The catalytic activity for the selective reduction was evahmted hi tenns of the N2 production as CNo = 2NJNO and for the oxidation of CHsOH and CH4 as CCH = COx/HC (CO and CO2 were flae only oxidation products). Cj conversions were evaluated upwards and downwards with temperature to test results.

699 NO selective reduction (HC + NO + Oz) mid oxidation (HC + O2) experiences were performed. Within the text, the former will be referred to as "reaction A" mad the latter as "reaction B", HC being equal to either CFL or CH3OH, as it corresponds. 3. RESULTSAND DISCUSSION 3.1. Methane as reducing agent

In the process of nitric oxide selective reduction, two maha reactions are hwolved: NO~ to N2 reduction, mad the oxidation of the hydrocarbon with oxygen. When the hydrocarbon employed is methane, the copper exchanged in ZSM5 is ineffective to reduce NO., since CFL preferably reacts with oxygen due to the great oxidathag activity of the extralattice oxygens in CuZSM5 [9]. Figure 1.a shows the results obtained for reactions (A) (CH4 + 02 + NO) mid (B) (CH4 + O2) when CuMordelfite is used as catalyst. In agreement with what has been reported for CuZSM5 [2], no reduction of NO to N2 is observed, the methmle conversions behlg shnilar hi both (A) and (B) reactions.

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350 400 450 500 550 600 650 Temperature

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Figure l . a : CH 4 + 02 + NO and CH 4 + O= Figure l.b: CH 4 + O 2 + N O and CH 4 + O 2 reactions over CuMordenite reactions over CoMordenite M e t h a n e conversion (CH 4 + 02 + NO), ---=--. M e t h a n e conversion (CH 4 + 02), -- NO conversion

700

Instead, when CoMordenite is used as catalyst (Figure 1.b) it is clearly seen that this one is active for NO reduction; besides, the methane conversion ha reaction (A) occurs at lower temperatures than hi reaction 03). The temperatttre at which NO reduction begins to appear hi Figure 1.b coincides with the begilming of CH4 conversion ha reaction (A). This behavior leads us to tlmak of two stages for the selective reduction of NO. In the first one, at low temperatures, CH4 oxidation promoted by the presence of NO• starts. The second one consists in the direct oxidation of CH4 with O2, and as a consequence of its consumption, the conversion of NO to N2 decreases. These two stages are consistent wifll the experhnental observations usually reported in the literature: the maxilnuln hi the conversion of NO to N2, and the promotion of HC oxidation due to the presence of NO. However, the first stage mentioned above, does not shnply consist ha the reduction of NO with HC, since by perfonning a mass balance for file CH4 consumed, it is deduced that there exists a catalytic effect of NO for the oxidation of HC with O2. Tiffs results from the observation of the fact that the alnotmt of HC reacting with 02 in reaction (A) is greater than the alnotmt of the same HC reaction with 02 ha reaction (13), be it NO or NO2 the reactant ha the mass balance. This comparison was perfonned in the low COlwersions zones of Figure 1, calculathag the amotmt of CH4 reacting with 02 ha reaction (A) as: CH4 moles totally converted minus CH4 reacted with NO• This same effect was observed when the hydrocarbon employed was ethylene [10]. The exception occurred when CuMordenite and CH4 were used (Figure 1.a), in which case NO does not react and both CH4 conversion curves coincide. These restdts may be explained through the existence of an oxygenated hydrocarbon as reaction intennediate, as proposed by Sasaki et al. [8]. According to this mechanism, HC would be partially oxidated at low temperatures (to methanol or fonnaldehyde if the hydrocarbon is methane), this compotmd behag easily oxidated by NO• or 02. The possibility of the catalytic effect of NO ha this partial oxidation stage is supported by the studies of McConkey and Wilkinson [11] who ilwestigated flae obtention of HCHO from CH4 and 02 using NO as catalyst ha homogeneous phase. The said authors propose a mechanism according to which NO2 dehydrogenates Ct-I4, producing methyl radicals which can be partially oxidated to fonnaldehyde. Sequemially, HCHO oxidates to CO• As already pohated out, the CuMordenite catalyst is haeffective to reduce NO with CH4 in the presence of oxygen, different from the CoMordenite behavior. This difference is consistent with the different redox capacity of these solids. Mir6 et al. [12] reported that the copper exchanged in mordenite can be totally reduced to Cu(I) when the reducing agent is carbon monoxide, and to Cu(0) when the reduchag agent is hydrogen, at temperatures lower than 300~ in both cases. On the other hand, cobalt exchanged with mordenite is very difficult of being reduced. Mir6 and

701 Pettmchi [13] reported no more than 15% reduction with CO or 1-/2 at 500~ Tiffs difference in the reduction capacity explahls why methane is easily oxidated by the extralattice oxygen fll the case of CuMordenite, this oxygen being returned from the gas phase hi a redox cycle, NO• remahah~g tmreacted, hastead, ha the case of CoMordenite, the more moderate oxidating capacity of this solid could allow the fonnation of oxygenated hatennediates for the subsequent NOx reduction.

50-

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~930tl} t.-

o 20

o

10

./.

0 350 400 450 500 550 600 650 Temperature (*C)

Figure 2: NO conversion in CH4 + NO reaction over CuMordenite --- and CoMordenite

111the absence of oxygen (CH4 + NO reaction) both catalysts, CttMordenite and CoMordenite present sflnilar conversion values (Figure 2). Taking hato account that these values have been obtahaed after approximately 30 minutes of reaction, it is possible that copper, due to the non-existence of oxygen in the gas phase, be partially reduced by methm~e. This reduction of copper could decrease its oxidath~g activity, rims allowhag the reaction of methane wifla nitric oxide. Under flae working conditions of Figure 2, the decomposition reaction of nitric oxide over CoM (without methmae) practically does not occur, h~ the case of CuM, NO decomposition occurs, but at lower conversions than the observed for CH4 + NO reaction. 3.2. Methanol as reducing agent With the object of stressing the possibility of an oxygenated compound as hatennediate of the selective NO reduction with methane, methanol was used as reduchag agent. Figure 3.b shows the results of methanol mad nitric oxide COlwersion at different temperatures for reactions A and B over CoMordenite. It can be observed that the conversion of nitric oxide to nitrogen beghas to occur at temperatures shnilar to those for tim selective reduction with methm~e. Tiffs fact clearly supports the

'/02

existence of an oxygenated compotmd ha the CH4 CoMorde~fite.

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(~

Figure 3.a: CH30H + NO + 02 and Figure 3.b: CH30H + NO + 02 and CH30H + 02 reactions over CuMordenite. CH30H + 02 reactions over CoMordenite. Methanol conversion (CH30H + 02 + NO), --4--- Methanol conversion (CH30H + 02), -- NO conversion

h~ the case of the CttlVlorde~fite catalyst, as stated before, no NO conversion is observed when CH4 is used as reducing agem due to the high oxidating capacity of fllis solid. Concemhag the role of a possible oxygenated intermediate hi fllis catalyst, two hypotheses may be forlnulated: methane is partially oxidated but the hltennediate is destroyed on the catalysts surface without reacting with the nitric oxide, or else methane oxidates to COx directly. The first hypothesis can be sustained wifll the values of the activation energies of the CH3OH + 02 reaction, calculated for CoM and CuM. For the first catalyst E = 48.3 kcal/mol was obtained, mad for CuM, E = 29.6 kcal/mol. These values indicate a greater stability oflnethanol over CoM. It seems reasonable then that in file case of file CoM catalyst, ml oxygenated intermediate may acquire a metal life thne enough to reduce nitric oxide, whereas ha CuM fllis possibility is smaller. However, the results shown ha Figure 3.a support the second hypothesis (direct oxidation of CH4 to CO• shlce it cma be observed flaat meflamlol reduces nitric oxide in the presence of oxygen, indicathlg that if file oxygenated intermediate were formed during the CH4 + NO + 02 reaction, NOx could favourably compete with oxygen to react with the said intermediate. The equilibritun between NO mad NO2, which might

703 be an intennediate, may also play an hnportant role in the reaction mechanisln. Further experiments are in progress in order to dilucidate this phenomenon. It is necessary here to draw attention on the way in which these experiments were conducted in what concerns to the oxygen feed. As already stated in the Experimental section, oxygen was incorporated to the gas phase very close to the catalyst bed. Experiences perfonned mixflag oxygen at the reactor inlet, showed lower nitric oxide conversions. This is due to the fact that methanol oxidation takes place in the reactor void volume before reaclfing the catalyst bed, thus obtaining NO conversions similar to those of the non-catalytic gas phase reaction. From the observation of Figures 3.a and 3.b, another interesting fact can be noticed. Colwersion of NO to N2 is produced at temperatures at which a 100% methanol conversion was already reached, that is, the conversion-temperature curves for the oxidation of methanol and for NO reduction are displaced approximately a DT of 100~ ha both CoM and CuM catalysts. This differs from what is nonnally observed with methane. This delay ha the NO reduction towards higher temperatures could be originated in the formation of a carbon deposit which would poison the sites necessary for NO adsorption. When an adequate temperature for the combustion of surface carbon with oxygen is reached (approxflnately 400~ the catalyst becomes active for NO reduction. A similar effect is proposed in [14] using propylene and propane as reducing agents. Halnada et al. [15] did not fred nitric oxide conversion ushlg methanol as reducing agent and CuZSM5 as catalyst, thus differing from our results. Probably this is due to the influence of the gas phase reactions mentioned above, or maybe these authors did not reach temperatures high enough to btma the carbon deposit. Figure 4 shows transient experiments perforlned with CoM mad CuM with the object of stressing the role of 02 on the CH3OH+O2+NO reaction. In those expeNnents, once the steady state was reached, the oxygen flow was haterrupted (marked as time = 0 hi the figure), thus decreashlg its concentration to negligible levels before the five milmtes of the transient exper/ment. The curves shown indicate that initially, when the surface is clean due to the presence of oxygen, there is an appreciable COlwersion level (40% for CuM mad 70% for CoM). When oxygen is eliminated, the rate of NO reduction slowly decreases until reachflag a new steadystate value which coincides with the one observed for the non-catalytic reaction, without oxygen, in the gas phase (Figure 5). This result supports the role of oxygen in maintainhag the surface clean of carbon deposits, since when 02 is interrupted, the reducing activity is mahatained for a time even though oxygen has disappeared fi'Oln the gas phase. Similar results were reported by Pettmchi and Hall (7) in their studies on the selective NO reduction with isobutane over CuZSM5. These authors fotmd coke forlnation and the reduction of Cu 2§ (disappearance of 100% of the Cu 2§ signal by gPR).

704

100 0~ 80 , - , - - , .s = 9 6O c: O

O z

I

40 2O

.

0 2 Cut

o~

,~,

Steady d State

20 4'0 6'0 8'0 160 1:20 Time (rain.)

Figure 4: Transient experiments over CoMordenite ---.-- and Cu Mordenite - e - . Oxygen is cut at time equal zero.

Figure 5 shows nitric oxide conversions at different temperatures for the NO + CH3OH and NO + CH3OH + 02 reactions in the gas phase.

50~ I

e--

._o

I 301

cO

" 20,i

oz

i

101 0

~ / ILl3

400

Figure 5" Gas phase reaction

~

~ CH3OH+NO CH3OH +NO +O 2

5()0 6(30 7()0 Temperature (~ In these experiments, the catalyst bed was replaced by a similar volume of quartz chips. It is hateresthag to observe that the NO conversions for both reactions are shnilar. Different from methanol, when mefllane or ethylene are used as reduchlg agents in the HC + NO + 02 reaction hi the gas phase, no nitric oxide conversion is observed [10]. These results seem to support the existence of a mechanism with oxygenated hatennediates, the production of these hltennediates via catalytic oxidation of HC with 02 or with NO2, behag a ftmdamental role of the catalyst. Once the hatenr~ediate has been fonned, its reaction with NOx could take place on the

705 catalyst surface or the gas phase as depicted in Figure 5. When the hydrocarbon is methanol, oxygen has already been filcorporated fiato the molecule, and the partial oxidation stage is not necessary. For tiffs reason, fi~ the gas phase reaction, oxygen does not noticeably impfiage on the NO to N~ COlwersion. When flae CH3OH + NO + O~ reaction is carried out through the catalytic way with CoM or CuM, the fundamental role of 02 would be to mafiltafil the surface free from carbon deposits.

4. CONCLUSION

The mahl conclusions from this study may be sturnnarized as follows" NO, besides behlg reduced hi the presence of 02 with CH4 or CH3OH over CoM, acts as a catalyst in the oxidation of the said reactants. CH3OH is a selective NO• reducing agent hi Cu and Co Mordelfite. The greater redox activity of CuMordenite, compared to that of CoM, would justify why the first solid does not selectively reduce NO,, with CH4. An oxygenated compotmd, of the CH3OH type when the reducfl~g agent is CH4, would act as an interlnediate in the case of CoM. Oxygen would perform the ftmction of maintaflm~g the catalyst surface free from carbon deposits.

ACKNOWLEDGMENTS

Fhlmltial support was provided by CONICET and UNL (CAI+D 162). We are indebted to Prof. Elsa Grhnaldi for her assistrmce hi the edition of the manuscript.

706 REFERENCES

T.S. Truex, R.A. Searle mad D.C. Sun, Plat. Met. Rev., 36(1) (1992). W. Held and A. Kolmag, Ger. Often, DE 3, 642018 (1989) assigned to Vokswagen. S. Sato, Y. Yu-u, H. Yahiro, N. Mixtmo mad M. Iwamoto, Appl. Catal., 70 L1 (1991). 4 R. Burch and P.J. Millhagton, Appl. Catal. B: 2, 101 (1993). 5 E. Kukuchi, K. Yogo, S. Tmaaka m~d M. Abe, Chem. Lett., 1063 (1991). 6 T./ami, S. Iwamoto, S. Kojo mid T. Yoshida, Catal. Lett., L3, 87 (1992). 7 J.O. Pettmchi mad W.K. Hall, Appl. Catal. B:2, L17, (1993). 8 M. Sasaki, H. Hmnada, Y. Kintaichi mad T. Ito, Catal. Lett., 15, 297(1992). 9 Y. Li, P. Battavio mad J. Annor, J. Catal., 142, 561 (1993). 10 J. Vassallo, E. Mir6 mid J.O. Pettmchi, tmpublished restdts. 11 B. McConkey mad P. Wilkinson, I & E C Proc. Res. Des. mad Dev., 6(4) 436 (1967). 12 E. E. Mir6, E.A. Lombardo and J.O. Pettmchi, J. Catal., 104, 176 (1987). 13 E.E. Mir6 and J.O. Pettmchi, J. Chem. Soc. Faraday Trmas., 88(8) 1219 (1992). 14 J. d'Itri m~d W. Sachtler, Appl. Catal. B:2, L7 (1993). 15 H. Hamada, Y. Kintaichi, M. Sasaki, T. Ito mad T. Yoshhaari, Appl. Catal. A: 88, L1 (1992).



707

SEPIOLITE BASED MONOLITHIC CATALYSTS FOR THE REDUCTION OF NITRIC OXIDE WITH PROPYLENE IN OXIDISING A T M O S P H E R E P. Avila, J. Blanco, J.M.R. Bias, O. Ruiz de los Patios and M.Yates. lnst. Cat6lisis y Petroleoquimica, Campus UAM, Cantoblanco, 28049 Madrid ABSTRACT This work deals with the analysis of the behaviour of new materials as catalysts for the selective reduction of nitrogen oxides in oxidising atmospheres. The catalysts were prepared using as the active phase oxides of copper and nickel, impregnated on different types of support whose principal component was sepiolite, a natural magnesium silicate. The catalysts were produced in the form of monoliths of 8 cells cm 2, to obtain solids with high thermal stability and excellent mechanical properties, with which NO conversions of greater than 75% were obtained when operating at an Area Velocity of 1.6 mh ~, with an 02 concentration of 8% by volume. Significant textural differences have been found between the solids which could affect to a certain extent the activity and selectivity of the catalysts in the studied reaction.

1. INTRODUCTION

Since Iwamoto et al. [1] and Held et al. [2] in 1990, published their first studies on the elimination of nitrogen oxides in oxidising atmospheres using hydrocarbons as selective reducing agents, there has been a substancial growth in the number of studies which have appeared in the literature on this process, fundamentally due to the necessity of finding a solution to the control of emissions from diesel engines. Most catalysts appearing in the literature since then are based on zeolites exchanged with transition metals, with those exchanged with copper the most active. Outstanding contributions have been made by Iwamoto et al. [3] and Hamada et al. [4] in tiffs field generally with zeolite H-ZSM-5 exchanged with copper, using various reductors. Latterly, a range of studies have been published ,This work was supported by the project numbers AMB 92-0190 and AMB 93-0244 of the Spanish CICYT.

708 which likewise use copper or copper oxide exchanged or supported on various materials [5,6]. Although great advances in the development of catalysts for the elimination of nitrogen oxides in oxidising atmospheres have been made, serious drawbacks still exist before their adoption in industrial applications due to the instability of the catalysts and the necessity of operating at high hydrocarbon:nitrogen oxide ratios. In this work the catalytic activity of a series of copper oxide catalysts supported on monolithic honeycomb supports in the reduction of nitrogen oxide with propylene in an oxidising atmosphere was studied. The monoliths were produced from acid washed sepiolite, sepiolite or a mixture of sepiolite and alumina in order to study the effect of the support on the activities and selectivities of the catalysts. The introduction of nickel oxide as a second active species on the overall activity was also determined. Finally the application of an alumina washcoat impregnated with the copper and nickel salts to increase the accessibility of the gases to be treated to the active phase was studied.

2. EXPERIMENTAL

The activity measurements were made in a continuous tubular reactor of 2.54 cm ID operating in an integral regime at a total pressure of 120 KPa. The NO and propylene inlet concentrations were 1000 ppm while the oxygen was varied between 1 and 8 vol.% with a nitrogen balance. The area velocity was varied between 1 and 5 mh ~ and the reaction temperature between 100 and 500~ Analysis of the inlet and outlet gas concentrations were made using specific analyzers for each gas. Thus, the NOx concentration was determined by chemiluminiscence with a Beckman mlalyser model 951A, the CO and COz, by nondispersive I.R. spectrometry in two Beckman model 880 analysers, the oxygen by paramagnetic analysis in a Beckman 755 analyser and the hydrocarbons by means of a Beckanan flame ionization detector model 400A. The textural characterization of the supports and catalysts: pore size distribution, pore volume, and surface areas were determined by use of mercury intrusion porosimetry using a Micromeritics Poresizer 9320 m~d nitrogen gas adsorption/desorption isotherms carried out on a Micromeretics ASAP 2000 respectively. For the porosimetry analysis a contact angle of 140 ~ and surface tension of 480mNm ~ for mercury were assumed. The catalysts were prepared on monolithic structures of parallel channels of square section with a density of 8 cells/cm2 and a wall thickness of 0.89 ram. Three types of monolithic support were used in this study: "ST" from sepiolite,

709 "SL" from sepiolite washed with a 2N HNO3 aqueous solution and "SA" from sepiolite and alumina (60 and 40 wt% respectively). All of these monolithic supports were subsequently heat treated at 500~ for 4 hours in an air atmosphere. The supported metal oxides which constitute the active phase of these catalysts were incorporated by impregnation on the support (SLCu, SLCuNi, STCuNi and SACuNi catalysts) or over a dispersion of alumina that was wash coated (5% by weight of the support) over the support (SA(RCuNi).


The results of this study have been divided into three sections. In the first the influence of the incorporation of nickel oxide on the catalytic activity of a copper catalyst was studied, the second deals with the ilffluence of the textural nature of the support while the third looks at the selectivity of the reduction of NO with propylene on changing the concentration of oxygen in the gas stream. 3.1 Effect of the incorporation of a second element in the active phase Taking as a reference the activity of the catalyst of copper oxide supported on sepiolite washed with an acid solution, SLCu, the influence of the introduction of a second metal, Co or Ni, maintaining the Cu:M ratio at 9:1 wt% was studied. ISLCu

100

o

S L C u . ~ ; ~ "~ .4r - 9 ,,. ~ - " SLCuCo I// It/

',,g ~,,

80

Iii Iii

E

,'/~

60 O O9 rr 40

Il I I i I t iI/~-...~

LL!

O 20 o 0 100

SLCuOo

200

300

400

500

REACTION TEMPERATURE,*C

Fig.1 Influence of the nature of the active phase on the conversion of NO ( ) and C3H6(-----)

710 In Figure 1 the conversion of nitric oxide (continuous lines) and propylene (dashed lines) v e r s u s the reaction temperature is presented. From this figure it may be observed that at temperatures below 280~ the propylene and nitric oxide react at a 1:1 molar ratio. At temperatures above this the oxidation of propylene begins to take place, due to the presence of oxygen (1% vol.) in the gas stream, with the subsequent separation of the two curves. Thus, the propylene conversion continues to increase with increasing temperature but the elimination of NO reaches a maximtnn at about 350~ and then progressively decreased. With respect to the effect of the incorporation of a second component on the activity, it may be observed that the catalyst which included nickel, SLCuNi, was appreciably more active than the catalyst of copper only, SLCu, over the whole range of temperatures. However, the catalyst of copper and cobalt, SLCuCo, gave rise to NO conversion values inferior to the copper catalyst over the whole temperature range. From these results it was clear that the incorporation of nickel was beneficial in both reactions. This increase was especially pronotmced in the reduction of nitric oxide where conversion values of 50% could be achieved working at an area velocity of 4.7 mh ~. Similar results to those discussed above have been obtained by Blanco et al. using natural gas as a reducing agent [7], operating with catalysts supported on alumina. R. Hierl et al. [8], studying these catalysts, found that "the presence of Ni 2+ in the catalyst leads to an enhaalced surface segregation of Cu z+ accompanied by an increased tetrahedral site population by Cu z+''. 3.2 Effect of the physical nature of the support Maintaining the concentration of the active phase constant (Cu and Ni), two further oxide based catalysts were prepared using as supports: sepiolite "STCuNi" and a mixture of sepiolite and alumina "SACuNi" respectively. These were compared with the catalyst described previously "SLCuNi" prepared on a support of sepiolite which had been washed with an acid solution. In Figure 2 the conversion of NO and propylene v e r s u s the reaction temperature in the conditions stated previously are presented. Taking as a reference the behaviour of the catalyst SLCuNi, described previously, it may be observed that when sepiolite treated at 500~ was used as a support there was an appreciable decrease in the selectivity of the catalyst towards the conversion of NO. From Figure 2 it may be seen that the NO conversion separated from that observed for propylene at a temperature between 200 ~ and 220~ Under these conditions the maximum value of NO conversion achieved was only about 30%. The catalyst prepared using a mixture of sepiolite and alumina as support "SACuNi", without doubt led to a pronounced increase in the activity compared

711

80

E

g

,/' " A""

60

CuNi

4o/ o

STCuNi

,r

"",.

"

I

20 0

20o

~ a0o

STCuNiJ

REACTIONTEMPERATURE,"C Fig. 2 Influence of the support on the activity of Cu-Ni catalysts. to the other two catalysts tested. With this catalyst NO conversion values of the order of 80% were reached. An attempt was made to explain the observed variations in the activities of the catalysts from their corresponding XRD and FTIR analyses, however, no marked differences in the spectra were observed. However, from the point of view of their textural characterization, the catalysts supported on mixtures of sepiolite and alumina possessed a porous structure which was markedly different from that of the catalysts supported on monoliths produced from sepiolite. In Table 1 the results obtained from the textural characterization of the supports and catalysts by nitrogen adsorption and mercury intrusion porosimetry are presented. In the table the values of surface area obtained from the gas adsorption results, using the BET method for which the linear portion was usually located in the relative pressure range of 0.05 to 0.3 SBE~[9], and those from the intrusion curve of the porosimetry analysis, using a nonintersecting cylindrical pore model S~, [10], are shown. The pore volume Vp is that recorded at the highest intrusion pressure reached during the porosimetry analysis, and as such represents the pore volume of pores between ca. 30gm to 3ran pore radius. The pore radii were taken from the maxima of the curves of pore size distribution. Taking as a reference the textural characteristics of the heat treated sepiolite support "ST", the data in Table 1 indicated that washing this natural silicate with an acid solution produced an appreciable increase in the BET surface area but had little effect on the surface area and pore volume measured by mercury porosimetry. Thus, this increase must have been in pores of between 1 and 3nm radius, since evaluation of the adsorption isotherln by use of the t-plot

712 [11], with a suitable standard, confinned that the material did not possess any microporosity. The increase in surface area in the small mesopores was possibly due to the removal of impurities and the reduction in alkaline and alkaline earth cations, notably Mg and Ca, by the acid treatment.

Table I Textural Properties of Supports and Catalysts

SBET (mE/g)

SHg (m2/g)

ST

124

82

0.489

18.1

......

SL

199

86

0.517

16.1

. . . . . .

SA

171

84

0.448

3.1

16.4

401.0

SLCuNi

133

104

0.552

14.2

SACuNi

132

91

0.432

6.0

18.3

326.8

SA(RCuNi)

135

124

0.495

3.1

17.4

549.0

Support

Vp (cma/g)

l'pore(1) l'pore(2) l'pore(3) (lain) (lun) (nm)

Catalysts

The incorporation of alumina into the support caused an apparent reduction in the total pore volume although the value of the BET surface area was located between that of the other two supports. This apparent fall in the pore volume was due to the fact that the alumina had a high volume of mesopores which were too small to be detected by the mercury porosimetry technique. Calculation of the mesopore volume of this material from the plateau in the desorption branch of the nitrogen isothenn at high relative pressure (p/pO = 0.95) gave a mesopore volume of 0.484cm3/g. The macropore volume of this material due to the interparticulate space between the alumina particles was 0.202cm3/g, which gave a true total pore volume of 0.686cm3/g. The most significant characteristic of the porosity in this material was the trimodal pore size distribution due to the characteristic porosities of the two base materials with maxima of pore diameters at 6, 18 and 400ran. The solids prepared from heat treated sepiolite (ST, SL and the catalyst SLCuNi) all gave a Type II isotherm for the adsorption branch with a narrow desorption hysteresis, designated as Type IIb by Sing [ 10]. The narrow hysteresis

713

was due to slit shaped mesopores which extend into the macropore range. The typical shapes of the isotherms obtained with these materials are shown in Figure 3 as that corresponding to the heat treated sepiolite support "ST".

o

25oJ-

I --ST --Alumina ---SA I

e

0 e

-

I

m 200 0 c~ 150
o ._.1

_

.l...i.r~"~ "~''~ ,.,..,q ..,,'," " 9

so

0

I

0.2

I

I

I

0.4 0.6 0.8 RELATIVEPRESSURE,p/po

1

Fig. 3. Nitrogen isotherms of monoliths produced from heat treated sepiolite "~JT'; "Alumina"and a mixture of a two "~JA": In the same figure, for comparison, the isothenn obtained for the Alumina support after heat treatment at 500~ is shown. The isotherm was of Type IV, corresponding to a mesoporous material i.e. having pores between 1 and 25nm pore radii. The pore size distribution, calculated using the BJH [12] method on the desorption branch of the isothenn, indicated that the majority of the mesopores in this material had a radius of 3nm. In the monoliths composed of a physical mixture of sepiolite-alumina (SA and SACuNi) the adsorption branch was of Type II but the desorption hysteresis was much more pronounced due to the presence of the mesopores of the alumina. The shape of the curve for these samples is shown as that corresponding to SA in Figure 3. The catalysts prepared on these supports had similar properties to those corresponding to the support used. From the results presented in Table 1 the modifications in the properties which were caused by the introduction of the active phase on the supports may be seen. Thus, on the introduction of the active phases on the acid washed sepiolite, SLCuNi, the BET surface area was reduced, probably due to blocking of the narrower mesopores. Due to the deposition of the active phases on the pore walls the areas calculated from the intrusion curves of

714

the porosimetry determinations, SHg, increased and also, surprisingly, the total pore volume, as measured by mercury porosimetry. The most significant characteristic of the catalyst supported on sepiolite/alumina monolith which was thought to lead to the greater catalytic activity was the trimodal pore size distribution of the material. This distribution was due to the combination of the porosities of the two support materials. The resulting monolith not only had a high BET area due to the alumina but also very wide macropores (400nm) which increased the accessability to the internal pore network. With the catalysts supported on sepiolite based monoliths the absence of these wider pores in conjunction with the high area velocities probably led to the lower activities of the catalysts. Although the SA supports had higher stu-face areas which could have led to a better dispersion of the active phases, as mentioned previously this was not noted by differences in the X-ray diffraction patterns.

3.3 Effect of Oxygen 100 80

,~.----- ,f, ,,"

SACuNi

o

E :~ 60

1% 0 2

0 O9 rr 40 w

/

> Z O 20 o

0 100

8% 0 2

200

300

400

500

REACTIONTEMPERATURE,~ Fig. 4. Influence of the concentration of 02 in the gas stream The principal object of this study was the development of catalysts which could achieve the selective reduction of NO in the presence of elevated concentrations of 02. One of the m o s t important parameters to be taken fiato account was the influence of the concentration of 02 on the activity of the catalyst. Following the results described previously in this paper, it was found that the catalyst supported on a monolith based on sepiolite/alumina, SACuNi, demonstrated a higher activity and selectivity in the studied reaction when the 01 concentration was of

715

the order of 1% vol. Thus, further work at higher 02 concentrations was based on this catalyst. When the concentration of O2 in the gas stream was increased there was a reduction in the selectivity of the process to NO conversion over the whole temperature range. In Figure 4 the activity results obtained with the SACuNi catalyst operating at two concentrations of 02 in the gas stream (1 and 8%) are presented. From the figure it may be appreciated that when the reaction took place in the presence of 1% Oz the conversion of propylene and NO followed a 1:1 molar ratio up to 280~ At higher temperatures the curves separated due to the reaction of the propylene with the 02 in the gas stream. The maximum NO conversion of 75% was reached at a temperature of 300~ When the Oz concentration was increased to 8% the separation of the conversion curves for propylene and NO occured at a lower temperature (210~ and the lnaxilnum NO conversion attained was only of the order of 40%. Also under these conditions the optimum operating temperature range was found to be narrower. 100 ,

o

A(RCuNi)

80

E

60 0 09 rr 40 LU > Z

0 0

.9

STP

20

0

100

7

,," 200

4.7 mh-ISTP 300

400

500

REACTION TEMPERATURE,~

Fig.5. Influence of the Area Velocity. The results obtained with SACuNi operating at 8 vol.% 02 improved when the active phases were introduced onto the monolith in the form of a washcoat SA(RCuNi). In Figure 5 the activity results obtained with this catalyst operating at two area velocities are presented. Of note were the NO conversions of greater than 75% at relatively low reaction temperatures (200-300~ Although the operating temperature range was narrow and the area velocities low, this result may be considered as encouraging in offering

716 alternatives to copper exchanged zeolites, nevertheless fi~rther work is required to improve the operating parameters.

4. CONCLUSIONS

From the results presented in this study it was found that the inclusion of nickel in the active phase caused a significant increase in the catalytic activity and selectivity of the catalyst in comparison to those with only copper. Catalysts supported on monoliths based on a mixture of sepiolite and alumina had much better selectivities to NO conversion than the corresponding catalysts supported on monoliths prepared from sepiolite. This was thought to be due to the different textural properties of these mixed composition supports, where the presence of wide macropores and the higher surface areas improved the accessibility of the reaction gases to the internal pore network. Increase in the concentration of 02 in the feed stock produced a marked decrease in the selective reduction of NO due to the combustion of the propylene. Not only was the maximum NO conversion reduced but the useful operating temperature range also became narrower. The incorporation of the active phases on to the monolithic support after first applying an alumina washcoat greatly increased the selectivity of the catalyst where NO conversions of 75% could be achieved. This was probably due to a reduction in any diffi~sional limitations.

717 REFERENCES

M. Iwamoto, Proc. of Meeting of Catalytic Teclmology for Removal of Nitrogen Monoxide, Tokyo, (1990) 17. W. Held, A. K6nig, T. Richter and L. Puppe, SAE Paper 900496 (1990). M. Iwamoto, H. Yahiro, S. Shundo, Y. Yu-u and N. Mizuno, Applied Catalysis, 69,(1991 ) L 15, L 19. H. Hamada, Y. Kintaichi and T. Yoshinari, Enviromental Industrial Catalysis, 1~tEuropean Workshop Meeting, (1992) 219. M. Iwamoto, N. Mizuno and H. Yahiro, Catalysis Research Center, (1992) 213. H. Hosose, H. Yahiro, N. Mizuno and M. Iwamoto, Chemistry Letters,(1991) 1859. J. Blanco and A. Martinez, Quimica e Industria, 22, 8, (1976) 855. R. Hierl, H. Kn0zinger and H-P. Urbach, J Catal., 69, (1981) 475. S. Brunauer, P.H. Enunett and E. Teller, J. Am. Chem. Soc.,60 (1938) 309. 10 H.M. Rootare and C.F. Prenzlow, J. Phys. Chem., 71 (1967) 2733. 11 B.C. Lippens and J.H. de Boer, J. Catal., 4, (1965) 319. 12 K.S.W. Sing, Third Intemacional Conference on Fundamentals of Adsorption, Engineering Foundation, New York, (1991) 67. 13 E.P. Barret, L.G. Joyner and P.H. Halenda, J. Amer. Chem. Soc., 73, (1951) 373.


Catalyst Aging and Poisoning



Catalysis and AutomotivePollution Control111


721

IMPACT OF SULFUR ON T H R E E - W A Y CATALYSTS: C O M P A R I S O N OF C O M M E R C I A L L Y P R O D U C E D Pd AND Pt-Rh M O N O L I T H S D. D. Beck and John W. Sommers Physical Chemistry Department General Motors NAO Research and Development Center Warren, M148090

ABSTRACT Commercially-prepared Pt-Rh and Pd monolith catalysts were thermally aged then characterized for catalytic performance using a laboratory reactor to evaluate the magnitude and reversibility of the impact of sulfur on three-way activity. The SO 2 concentration in the feedstream was varied from 0 ppm to 30 ppm, which was comparable to sulfur levels in gasoline ranging from 0 to 450 ppm. Tests were first conducted using propylene and repeated using propane to represent the hydrocarbon mixture in exhaust. Of the two catalysts, Pd showed better propylene lightoff activity while Pt-Rh showed better propane lightoff activity, regardless of the sulfur content. For each catalyst, increasing the sulfur concentration from 0 ppm SO 2 to 30 ppm SO 2 of sulfur resulted in a lightoff temperature increase by 40 to 60~ Under warmed-up conditions, the loss of activity for HC, CO and NOx due to the presence of sulfur was greater under slightly rich conditions than under lean conditions for both Pd and Pt-Rh, while the magnitude of the impact on NOx and particularly on HC activity under warmed-up stoichiometric conditions was significant and much greater for Pd than for Pt-Rh catalyst. Using propylene, the effect of SO 2 on the activity of the Pd catalyst was partly reversible, while the effect on Pt-Rh was completely reversible. Using propane, the effect of sulfur on the activity of both catalysts was larger than for propylene. The resulting decrease in activity due to the presence of sulfur was partly reversible on Pt-Rh, but the poisoning of the Pd catalyst was mostly irreversible. Part of the irreversible poisoning effect is attributed to a direct interaction or reaction between SO 2 and Pd, while the other part is attributed to the promotional effect of SO 2 in hydrocarbon coking of the catalyst when alkane hydrocarbons are present.

722 1.INTRODUCTION Organo-sulfur compounds are commonly present in nearly all commercially produced gasoline blends which are intended for vehicle use. These compounds are involved in the combustion process in the engine and are converted mainly into sulfur dioxide before entering the catalytic converter or converters. This form of sulfur has been demonstrated to deactivate vehicle exhaust catalysts. Prior work performed in the 1970's focused on the impact of sulfur on Pt and/or Pd supported on alumina catalysts operating under net oxidizing, or "lean" conditions [ 1-3]. Currently used three-way catalyst systems are far more complicated in that their washcoat formulations contain in addition to Pt, Rh, and sometimes Pd noble metals, a number of base metal oxides of Ce, La, Ni, Ba, Fe, Nd, and others. The exhaust adds to the complexity by cycling rapidly between net reducing and net oxidizing conditions when the vehicle operates trader closed loop control. The cycling between these conditions may not be balanced under certain operating conditions such as a quick acceleration or deceleration or when a load condition is imposed. Moreover, the vehicle calibration may be slightly biased toward net lean or net rich operation. All of these conditions influence how SO2 in exhaust interacts with the support, base metal oxides, and noble metal components in the catalyst and, in turn, affects activity. Laboratory studies of the effect of sulfur on three-way activity showed that activity was inhibited particularly under rich conditions and mostly for catalysts containing both Pt and Pd, but activity was not significantly affected when the feedstream was cycled about a net stoichiometric point [4-6]. Sulfur has been demonstrated to poison the water-gas shift reaction and steam reforming reactions, [6-7] which is more important during operation under net stoichiometric or rich conditions since the availability of oxygen under these conditions is limited (HC and CO are easily removed by simple oxidation under lean conditions). It is also known from surface science studies that SO 2 dissociates on Pt, Rh, and Pd, forming adsorbed oxygen and adsorbed sulfur, the latter being difficult to remove in rich conditions [8-13]. Small coverages of elemental sulfur can significantly poison the noble metal surface for the adsorption of adsorbates such as CO [13]. Vehicle studies indicated that sulfur deteriorates the performance of tluee-way catalysts [ 14], and the magnitude of the impact was found to be calibration-dependent [5,15]. When three-way catalyst formulations began incorporating larger amounts of Ce (up to ~30 wt.% Ce) to provide a number of beneficial effects, including the enhancement of the AfF "window" in which three-way activity occurs, H2S emissions in the exhaust became noticeable. These events prompted a number of studies of the mechanism of H2S formation in three-way catalysts to suggest

723 methods of inhibiting the release of sulfur as H2S in large "pulses". These studies showed that sulfur stored by the catalyst under net lean conditions was released under rich conditions [16]. Storage in lean conditions involves absorption and even reaction with the support and/or base metal oxide to form sulfates and sulfites [17,18]. Some of these species are strongly bound to the support and may be formed by the noble metal catalyzed oxidation of SO2 to form SO3 -2 [9,10]. Previous studies have also shown that the uptake of SO2 on CeO2 is far greater than on A120 3, ft~her pointing to the role of CeO 2 in the storage of sulfiar [16,19]. In reducing conditions, removal of sulfur occurs and involves reduction to H2S, elemental sulfur, and reaction with CO to form COS. In Pt-Rh catalysts, the storage and removal of sulfur can be at least partially inhibited by a variety of methods, including the processing of the catalyst to reduce the amount of sulfur stored by the base metal oxide components, or adding a scavenging agent such as Ni or Cu [ 19-23 ]. The study of the impact of sulfur on three-way systems has recently gained interest again, as attention has turned to the reformulation of gasoline to reduce vehicle emissions as called for by the Clean Air Act amendments of 1990 and new regulations imposed by the state of California. One of the issues taken up by the Auto-Oil Industry Air Quality Study has been the effect of fuel sulfur on FTP converter efficiency in two vehicle fleets, one comprised of vehicles manufactured between 1979 and 1986, the other of vehicles manufactured in 1989. Both fleets showed a significant improvement in emissions when the sulfur content in fuel was reduced, leading to a recommendation that gasoline reformulation should include a reduction of sulfur level [15,24]. These and other vehicle studies also showed that the effects of sulfur are generally reversible when the fuel was changed from a relatively high sulfur content to a low sulfur content [25]. Ultimately, vehicle studies such as these are needed to better determine the effect of various sulfur content fuels and operating conditions on catalyst performance, but laboratory studies can provide a better understanding of sulfur storage, release and poisoning mechanisms and effects under wellcontrolled conditions to help in the design of these vehicle tests. Such studies have been carried out in our laboratory using newer technology three-way catalyst systems employing Pt and Rh [ 13, 26]. Recent attention has been placed on the use of Pd-based catalyst formulations because of their ability to catalyze the oxidation of hydrocarbons and CO at relatively low temperatures as a strategy to improve cold-start emissions and thus comply with low emission vehicle regulations, and because of the lower cost of Pd metal relative to Pt and especially Rh [27-32]. Three-way catalysts using Pd or Pd and Pt were evaluated in the late 1970's and early 1980's, but were found to be easily poisoned by sulfur [33,34]. Indeed, recent studies

724

conducted in this laboratory have confirmed Pd-containing catalysts were particularly susceptible to irreversible sulfur poisoning trader isothermal exhaustlike conditions when compared to similar catalysts consisting of Pt and Rh supported on alumina [26, 36]. Recent developments in Pd catalyst teclmology have been demonstrated to improve the durability of the low temperature lightoff properties of this catalyst after repeated exposure to relatively high temperature exhaust [30,32,35]. Thus, these new catalyst formulations show promise for application as a close-coupled catalyst which can reach HC lightoff rapidly after cold-start. These new formulations may also be more resistant to sulfur poisoning. The effect of SO2 on these Pd catalyst formulations, however, has not been widely discussed in the published literature; thus the present study was performed to gain a better understanding of how sulfur affects the performance of a current production Pd catalyst intended for use in high temperature (up to 1000~ conditions such as a close-coupled converter, and how the impact of sulfur compares to a current teclmology Pt-Rh three-way converter having a similar noble metal loading. Changes in lightoff and isothermal performances were measured as a fimction of increasing SO2 concentration in a simulated exhaust feedstream using a laboratory reactor. Tests were first conducted using propylene as a model of the hydrocarbon species in exhaust, and then repeated using propane in a similar fimction. Additionally, the effect of sulfur on the performance of the catalysts during an air/fi~el ratio scan was also evaluated.

2.EXPERIMENTAL ASPECTS

2.1 Catalysts Two catalyst formulations were used in this study. The first, a Pd catalyst having a loading of 50 g/ft. 3 (0.29 wt.%), was obtained in monolith form (cell density 400 cells/in3). This washcoat formulation is considered to represent a state-of-the-art Pd catalyst for use in a rapid HC lightoff close-coupled (within 10-15" of the exhaust manifold) converter, and has been processed with several additives which serve to promote the activity of the Pd and to thermally stabilize the support and supported metal. The Pt-Rh monolith catalyst was also obtained in monolith fonn, having a cell density of 400 cells/in 3 and a loading of 23.5 g/fi3 Pt, 1.68 g/fl3 Rh (0.13 wt.% Pt, 0.0093 wt.% Rh). This washcoat is designed for use in converters which will be exposed to exhaust temperatures consistent with an underfloor location (at least 25-30" from the exhaust manifold), which are significantly lower than those encountered in a close-coupled location.

725

2.2 Thermal Aging Treatment All of the catalysts were evaluated following a thermal aging treatment. The thermal aging was performed by placing the sample in the center of a tube furnace and downstream from a heat exchange zone. In this apparatus, the catalyst is heated mainly by the treatment gases which pass through a heat exchanger. Constant treatment temperature was maintained at a constant value using a thermocouple contacting the catalyst bed to control the fiamace. The aging treatment consisted of alternating the gas feed between 5% O2/N2 and 5% H2/N 2 at a rate of 0.1 Hz while maintaining the temperature of the catalyst at 1000~ for 4h. 2.3 Activity Measurements Both Pd and Pt-Rh catalyst formulations were evaluated for lightoff and isothermal activity using a laboratory reactor [37]. The composition of the feedstream was chosen to simulate vehicle exhaust, and the composition was controlled using a computer which has been interfaced with a bank of mass flow controllers. In the first series of tests, propylene was chosen to represent the alkene hydrocarbon species in the emissions as it is one of the most abundant hydrocarbon species in exhaust [38] and it figures significantly in the determination of total NMOG emissions since its reactivity factor is relatively high. The tests were repeated using propane to represent the alkane hydrocarbon mass emissions as the alkanes are believed to be among the most difficult of all hydrocarbons in vehicle exhaust to oxidize catalytically. The reactor is configured with a computer-controlled switching valve which alternates between a net reducing feedstream composition and an oxidizing feedstream composition so that the dynamic characteristics of exhaust produced by a vehicle operating under closed-loop control are simulated [37]. For lightoff testing, a sample was first prepared by cutting a section of the monolith having a facial dimension of 10 x 10 cells and a length of 1", was then thermally aged, then loaded into the reactor and stabilized in a nitrogen flow for 1 h at 100~ and finally exposed to the simulated exhaust at 9 1/min while the temperature was decreased from 600~ to 100~ at 20~ Evaluations were performed using a feedstream which cycled about the stoichiometric point at A/F =14.1 with an amplitude of +0.5 A/F and a cycling frequency of 0.5 Hz. The sulfur level was held at a constant level during each lightoff test, but was changed between tests to determine the effect of sulfur on lightoff. The gas composition used for the lightoff tests is listed in Table 1. Isothermal tests were performed using the same samples, which were stabilized in a nitrogen flow for 1 h at 500~ prior to exposure to the simulated exhaust feed. During the isothermal test, the sulfi~r concentration was step-

726 changed from 0 ppm to a predeterlnined level for 15 min, then step-changed to 0 ppm for an additional 30 min to determine the effect of sulfi~r on wanned-up activity and to deterlnine the reversibility of the effect.

Table 1. Laboratory Reactor Simulated Exhaust, Cycled about Stoichiometry (Lightoff and Isothermal Tests) Gas Component 02

propylene (or propane) CO NO H2 H20 CO2 SO2 N2

Concentration 0.6 % (net) 1 300 ppm 0.77 % 500 ppm 0.2% 10.0 % 10.0 % 0,10, 20, or 30 ppm balance

1. The oxygen composition was switched between 0.2% 02 and 1.0% 02 every second.

Table 2. Isothermal Stoichiometry Scan Test Gas Component 02 propylene (or propane) CO NO H2 H20 CO2 SO2 N2

Concentration 0.20 % (net) to 1.0% (net) 1 300 ppln 0.77 % 500 ppm 0.2 % variable 10.0 % 10.0 % 0,10, 20, or 30 ppm balance

1. During this test, the oxygen composition was switched between a value lower than net and a value greater than net. During the scan, both values increase such that the net oxygen composition is increased from 0.2% to 1.0% in steps. Additional tests were perforlned in which the net stoichiometry was scanned

727 from a net reducing feedstream (A/F = 14.1) through stoichiometry (A/F = 14.6) to a net oxidizing feedstream (A/F = 15.1) at a given catalyst temperatm'e. This test, sometimes called an A/F ratio sweep test, closely models the exhaust of a late model 3.8 L V-6 engine operating under closed-loop control (the gas composition used for this test is listed in Table 2). During this test, a cycling amplitude of + 0.5 A/F and a cycling frequency of 0.5 Hz was used. These tests were performed to determine the impact of sulfur on catalyst activity as a function of feedstream stoichiometry. The exhaust gas concentrations and conditions used for all three of these tests are discussed in more detail elsewhere [35-37].

3.RESULTS AND DISCUSSION 3.1 Effect of Sulfur on Lightoff

The effect of sulfur dioxide on lightoff at stoichiometry of the thermally aged 0.29 % Pd catalyst is shown in Figures 1 and 2 using propylene and propane, respectively, to represent the hydrocarbon in the simulated exhaust feedstream. For the purpose of this work, lightoff activity is defined as the temperature at which 50% conversion efficiency occurs for a particular reactant. The lightoff activity was first obtained using a feedstream with no sulfur dioxide added. This experiment was repeated several times, using a different concentration of sulfur dioxide in the feedstream with each experiment. Lightoff activities were thus obtained using 10 ppm, 20 ppm, and 30 ppm sulfur dioxide. These particular sulfur concentrations were chosen as they represent realistic sulfur levels in current available fuels, approximately 150 ppm, 300 ppm, and 450 ppm, respectively [35,36]. As will be discussed later, each experiment was followed by a high temperature treatment in which the SO2 was removed from the feedstream, and the sample temperature was increased to 700~ where it remained for 30 min, followed by cooling to 500~ This treatment was found to restore the catalytic activity to the level originally measured prior to exposure to any SO2. The results obtained using either propylene or propane consistently show an increase in lightoff temperatures of HC, CO and NOx as the sulfur content in the feedstream is increased. The magnitude of the increase in the propylene and CO lightoff temperatures was on the order of 40~ as the SO2 content was increased from 0 ppm to 30 ppm, while the increase in the propane and CO lightoff temperatures was on the order of 60~ for the same increase in SO2 concentration. Regardless of the type of hydrocarbon used, the increase in the lightoff temperature of HC and CO appeared to be non-linear with increasing sulfur concentration: most of the increase in the lightoff temperature occurred when the SO2 concentration was increased from 0 ppm to 10 ppm, while a

728 smaller increase in the lightoff occurred with fitaher increase in the SO 2 concentration from 10 ppm to 30 ppm. The NOx activity was markedly lower than HC or CO, and adding even small amounts of SO2 resulted in the failure to reach the 50% conversion efficiency over the range tested (200 to 500~ However, in comparing the activity profile over this temperature range, one can conclude that the NOx activity was also significantly affected by the presence of SO2. We note that upon adding 10 ppm of SO2 to the simulated exhaust, not only the beginning of the catalyst lightoff was increased (by roughly 40~ using propylene and 60~ using propane), but the warmed-up activity at 500~ was also decreased by roughly a factor of 2 using either hydrocarbon when the SO2 concentration was increased from 0 ppm to 30 ppm. For NOx, most of the increase in the beginning of lightoff occurred upon increasing the SO2 level from 0 ppm to 10 ppm, whereas further increases in SO2 resulted in smaller increases in the temperature at which lightoff begins. Although not indicated in the figures, the magnitude of the effect of SO2 on lightoff activity is larger than the effect of the thermal aging procedure on activity. The thermal aging procedure used in this study has been found to generally cause a 30-35~ increase in CO and HC lightoff temperature. Similar lightoff tests were performed with the thermally aged 0.13% Pt, 0.0093% Rh production catalyst. In this case, the results obtained using either propylene (Figure 3) or propane (Figure 4) also consistently show an increase in lightoff temperatures of HC, CO and NOx as the sulfur content in the feedstream was increased. The magnitude of the increase in the propylene, CO, and NOx lightoff temperatures was on the order of 40~ as the SO2 content was increased from 0 ppm to 30 ppm. When propane was used as the hydrocarbon, the increase in the propane lightoff temperature was on the order of 40~ while the increase in the CO and NOx lightoff temperature was on the order of 60-70~ for the same increase in SO2 concentration. Regardless of the type of hydrocarbon used, the increase in the lightoff temperature of HC and CO was also found to be nonlinear with increasing sulfur concentration. For experiments conducted using propylene for the hydrocarbon, nearly all of the increase in the lightoff temperature occurred when the SO2 concentration was increased from 0 ppm to 10 ppm: further increases in the SO2 level up to 30 ppm resulted in very little additional increase in the lightoff temperature. For experiments in which propane was used, the increase in the lightoff temperature with but still very non-linear. Although not indicated on the figures, we note that the effect of sulfur on the lightoff performance was comparable to the effect due to the thermal aging treatment used in this work.

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Temperature (C) Figure 2. Lightoff curves for a thermally aged Pt-Rh catalyst sample using propylene as a hydrocarbon surrogate. Each curve was obtained using a different sulfur dioxide concentration in the synthetic exhaust feedstream. The dashed line was the result of a lightoff test using 30 ppm sulfur dioxide in the feedstream which was repeated using 0 ppm sulfur dioxide in the feedstream. Because the Pt-Rh catalyst formulation was intended for positioning in an underfloor location in the vehicle, it is therefore not optimized for high temperature operation, and the high temperature aging treatment we used may have deteriorated the perfonrmnce of the commercial Pt-Rh catalyst to a greater degree than the performance of the Pd catalyst, which has been formulated for operation at higher temperatures. Even considering this potential difference in the

731 aged catalysts, a comparison of the lightoff performance of the thermally Pd catalysts vs. the Pt-Rh catalyst with no sulfi~r in the feedstream does point out a clear advantage of the Pd catalyst for reducing cold-start alkene hydrocarbon mad CO emissions. Although the Pt-Rh catalyst shows better lightoff performance for alkane hydrocarbons in this comparison, the alkenes figure more prominently in the contribution to overall NMOG since they are more abundant and have higher reactivity factors; this is one of several reasons why Pd-based catalyst technology holds promise for use in close-coupled converter applications. We note with interest that the non-linear relationship between the SO 2 concentration and the magnitude of the impact on lightoff performance for both Pd and Pt-Rh based catalysts is characteristic of the effect of sulfur on monolithic three-way catalysts observed in previously reported laboratory [26] and vehicle studies [24]. Both studies showed that as the sulfi~r content was increased, the degradation in the lightoff or wanned-up emissions increased at a high rate initially, but became more gradual at higher sulfur levels, suggesting that very small amounts of sulfur in the exhaust can have a sigaaificant effect on emissions. In a more recent laboratory study, the relationship between the concentration of SO2 and the magnitude of the effect on the activity of model Pd catalysts (Pd supported on alumina alone or in the presence of one promoter such as ceria or lanthana) was found to be linear for CO and HC activity, although we note that the model catalysts used in that study were pelleted, not monolithic. Differences in mass transfer effects and the distribution of noble metals in pelleted vs. monolith catalysts may account for the linear effect of sulfur on pelleted catalysts vs. the non-linear effect of sulfur in monoliths. We note that the vehicle studies, in which the non-linear effect was also observed, were also conducted primarily with monolith catalysts. For all of the aged catalysts, an additional lightoff experiment was performed with no SO2 in the feedstream following the lightoff experiment using 30 ppm SO2. The results, shown in dashed lines in Figures 1-4, shows a decrease in the lightoff temperatures from the 30 ppm SO2 experiment for both Pd and PtRh type catalysts, but only partial recovery of activity (relative to the catalyst prior to exposure to SO2) has taken place with the Pd catalyst, whereas nearly complete recovery of the original activity has taken place with the Pt-Rh catalyst. This result, which was also observed in a prior study of the effect of SO2 on model Pd catalysts [36], further emphasizes the non-reversibility of sulfur poisoning in Pd catalysts, even for a state-of-the-art formulation, compared to the complete reversibility of the effect of sulfur in Pt-Rh three-way catalysts. We have speculated that the non-reversible sulfur poisoning of Pd is related to a

732 direct reaction between adsorbed S and the supported Pd metal, perhaps leading to the formation of a surface PdS compound [36], or possibly migration of S into the bulk of Pd. We have obtained evidence for the latter in studies of S02 adsorption on Pd foils [39], but further study is needed to better understand this phenomenon. 100 80 "60 .40 -. 2O v ~' 0 C ,,..,

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The effect of sulfur dioxide on the isothermal (500~ or "wanned-up" activity in which the exhaust was cycled about stoichiometry is shown in Figures

734 5 and 6 for thermally aged 0.29% Pd catalyst, first using propylene and then propane, respectively, to represent the HC in the exhaust. For this experiment, no SO2 was present for approximately 5 min, then the SO2 concentration was increased in a step-change to a desired level (10, 20 or 30 ppm) where it remained for 15 min. Following this, the SO2 was removed from the feedstream and the activity measurement continued for an additional 25-35 min. This experiment was repeated several times, using a different concentration of sulfur dioxide in the feedstream with each experiment. Wanned-up activities were thus obtained using 10 ppm, 20 ppm, and 30 ppm sulfur dioxide. After each test, the SO2 was removed from the feedstream, and the sample temperature was increased to 700~ where it remained for 30 min, followed by cooling to 500~ This treatment was found to restore the catalytic activity to the level originally measured prior to exposure to any SO2. When propylene was used to represent the HC in this test (Figure 5) the results obtained for the 0.29% Pd catalyst indicate that when the sulfur level in the feed was increased, a gradual decrease in the activity was observed for HC, CO, and NOx. The absolute magnitude of the decrease was large for CO and NOx: an increase in the SO2 concentration from 0 ppm to 30 ppm resulted in a decrease in CO conversion from 70% to 55% and in the NOx conversion from 65% to 30% after 15 min exposure to sulfur. Increasing the SO2 concentration from 0 ppm to 30 ppm resulted in a decrease in the HC conversion from 98% to 95%, which in absolute magnitude does not appear to be as large an effect as with CO or NOx, but we note that the 3% decrease in HC conversion translates into an increase in HC breakthrough of 150%. The rate of the decrease in conversion efficiency for HC, CO and N0x slowed considerably aider 15 min of exposure, but had not yet reached a stable level at this point. When SO2 was removed from the feedstream, the HC activity appeared to return to near its original level, but the recovery of CO and NOx activity was incomplete, even following an exposure of 30 min in a "clean" feedstream. Although not shown, when the experiment was allowed to run for 3 h, very little additional recovery took place. Similar experiments with the 0.29% Pd catalyst were performed using propane to represent the hydrocarbon (Figure 6). Again, a gradual decrease in the HC, CO, and NOx activity was observed, although the rate of poisoning did not change during the 15 min exposure to sulfur in the feedstream, and therefore equilibrium was not achieved. Note also that the magnitude of the decrease in activity was significantly larger for propane than for propylene: for instance, exposure to 30 ppm SO2 resulted in an 18% decrease in HC conversion, translating into a--200% increase in HC breakthrough. Decreases in the CO (by 45%) and NOx (by 50%) were also more significant than that observed when

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Figure 6. Isothermal (500~ activity of the thermally aged Pd catalyst using propane as a hydrocarbon surrogate. In these experiments, the sulfur dioxide concentration is maintained at 0 ppm for 5 min, then increased to either 5, 10, 20 or 30 ppm for 15 min, then decreased to 0 ppm for an additional 45 min.

propylene was used to represent the hydrocarbon (15% and 40%, respectively). It is also important to point out that when sulfur was removed from the feedstream, very little recovery of activity took place, indicating that most of the poisoning is irreversible at this temperature. The reason for the absence of a change in the

737 poisoning rate over the 15 min exposure period together with the dominance of the irreversible poisoning has yet to be identified, but at present we attribute part of this effect to hydrocarbon coking of the catalyst which is promoted by the presence of SO2 in the feedstream. In Figure 7, we show the effect of SO2 on the warmed-up activity of the thermally aged 0.13% Pt, 0.0093% Rh production catalyst using propylene to represent the hydrocarbon. For this catalyst, the presence of SO2 in the feedstream resulted in a more instantaneous decrease in the HC, CO, and NOx conversion efficiencies, but the magnitude of the decrease was dramatically lower than observed with the 0.29% Pd catalyst exposed to the same level of sulfur. For example, exposure to 30 ppm SO2 resulted in a decrease of roughly 1% in the HC conversion, translating to an increase of 30% in HC breakthrough. Decreases of 20% in the CO, and 30% in the NOx conversions were also observed. Moreover, when SO2 was removed from the feedstream, near complete recovery of the activity occurred within 15-30 min. The relative instantaneous behavior of poisoning as well as the complete reversibility were found to be consistent with those of a similar laboratory study in which the effect of SO2 on a three-way PtRh commercial monolith catalyst was compared with the effect on a commercial Pt-Pd-Rh pelleted catalyst [26]. Finally, in Figure 8 we show the effect of SO2 on the wanned-up activity of the thermally aged 0.13% Pt, 0.0093% Rh production catalyst using propane to represent the hydrocarbon. For this case, the presence of sulfur at 30 ppm resulted in a larger decrease in the HC conversion efficiency, from 86% to 68%, translating into an increase in HC breakthrough of ~200%, while the impact on the conversion efficiencies of CO (97% to 80%) and NOx (92% to 75%) was smaller than when propylene was used as the hydrocarbon. Removal of sulfur from the feedstream did lead to recovery of most (~60%-70%) but not all of the original activity after exposure to a sulfur-free feedstream for 30 min. The incomplete recovery of activity observed with both the Pd and Pt-Rh commercial samples when propane was used as the hydrocarbon suggests coking of the catalyst is important. Further evidence for this rationalization was obtained by observing that treatment of the Pt-Rh catalyst ha a net lean (1% 02) feedstream at 700~ resulted in near complete recovery of activity. Similar treatment of the propane-exposed Pd catalyst resulted in partial recovery of activity, whereas subsequent treatment in a net rich feedstream at 700~ resulted in complete recovery of the original activity. Our findings that SO2 enhances hydrocarbon coking (when propane is present in the feedstream) is consistent with earlier reports that SO2 can increase the acidity of supports such as alumina, and thus enhance the role of this support as an acid catalyst in hydride abstraction from alkanes such as propane, which then leads to a number of different reactions

738 including polymerization and further dehydrogenation. The resulting carbonaceous material is partially hydrogenated (so called "reversible" coking [40]) since it can be removed by oxidation. This coking phenomenon has been commonly observed on acid catalysts used for steam reforming [41,42]. 3.3 Effect of Sulfur on P e r f o r m a n c e as a Function of Stoichiometry

Both thermally aged catalysts were evaluated using tests in which the net stoichiometry was scanned from a net reducing fccdstream through stoichiometry to a net oxidizing feedstream at a catalyst temperature of 500~ These tests were first performed without sulfur in the feedstream and then repeated with 30 ppm SO2 in the feedstream to determine the impact of sulfur on catalyst activity as a function of stoichiomctry. Figure 9 shows the HC, CO and HOx conversion efficiencics for the aged 0.29% Pd catalyst as a function of mean air/fi~el ratio at 500~ using a test in which the net stoichiomctry was scanned from a net reducing feedstream through stoichiometry to a net oxidizing feedstream. For this case, propylene was used to represent the hydrocarbon. These tests were performed first with no SO2 and repeated with 30 ppm SO2 in the fecdstream. In the oxidative, or 'lean" exhaust environment between mean A/F ratios of 15.1 to 14.7, the presence of SO2 results in a slight decrease in the conversion efficiency for HC, CO and NO• Below a value of 14.7, the presence of sulfur results in a slight decrease in the CO activity which continues until a rich extreme of 14.1 in A/F ratio. The effect of SO2 on the conversion efficiencies of HC and NO• however, was significant below an A/F ratio of 14.7 and increases with decreasing mean A/F until the "rich" extreme of 14.1 was reached. Thus, the degree of the impact of sulfur on HC and NOx conversion efficiency is greatest under stoichiometric and "rich" operating conditions. The maximum impact of 30 ppm SO2 in terms of breakthrough in HC and NOx occurred at a mean A/F ratio of 14.3 to 14.2. At this point, the HC breakthrough increased by 600-700% while the NOxbreakthrough increased by 400-500%. This behavior was also observed in a similar study of the effect of SO2 on model Pd three-way catalysts [36] and is consistent with suggestions that SO2 directly poisons the noble metal surface in rich conditions [ 13]. Figure 10 shows the HC, CO and NO• conversion efficiencies for the thermally aged 0.29% Pd catalyst as a function of mean air/fuel ratio at 500~ using propane to represent the hydrocarbon. For reasons stated earlier, the extent of the effect of sulfur on catalyst activity was difficult to determine due to the inability to reach equilibrium when sulfur was added to the feedstream.

739

100 ;'

-'

,

1

HC 90

~ '

v

80

o

100

o - . .

Q~

80

E-

60

c

40

~9 (1) >

20

o

100[.

>,

c r

uJ O

C O

u

10 ppm 20 ppm 30 ppm

.

80~

6O

40 20

~

baseline (0 ppm) 10 ppm 20 ppm 30 ppm

9

,,

9

/10

~__

,

.

m

CO

-

NOx

t

9

ppm ,g--

-\ \ 20 pp~ 30 ppm

~o " ~o Time (minutes)

,:o

50

Figure 7. Isothermal (500 ~ activity of the thermally aged Pt-Rh catalyst using propylene as a hydrocarbon surrogate. In these experiments, the sulfur dioxide concentration is maintained at 0 ppm for 5 min, then increased to either 5, 1O, 20 or 30 ppm for 15 mm, then decreased to 0 ppm for an additional 45 min.

740

100~ 90

~ ~

/

baseline (0 ppm) --

HC -

30 ppm

0--9. V

O t-ohm

tO oum

UJ tO

L_

> cO

o

50

-

100

-

"

.

,

.

I

a

I

r

8060-

30 ppm

40200

i

9

9

i

9

|

i

I

i

100 80 60 40

"

20 0

0

9

'

10

i

I

20

20 ppm 30 ppm i

I

30

i

I

40

50

Time (minutes)

Figure 8. Isothermal (500~ activity of the thermally aged Pt-Rh catalyst using propane as a hydrocarbon surrogate. In these experiments, the sulfur dioxide concentration is maintained at 0 ppm for 5 min, then increased to either 5, 10, 20 or 30 ppm for 15 mm, then decreased to 0 ppm for an additional 45 min. Consequently, when 30 ppm SO 2 w a s added to the feedstream, the A/F ratio scan experiment was repeated several times until the result was found to reproducible within 5%, but we note that the full impact of sulfur on activity is probably larger. As indicated in the figure, we also found that the first scan from a lean to rich A/F

741 ratio produced a different result in the propane conversion than a first scan from a rich to lean A/F ratio when SO2 was present. Repeated A/F ratio scans resulted in the lower curve showing relatively constant propane conversion of 40-50% over the entire A/F ratio range tested. Thus, operation in a rich exhaust containing propane and SO2 results in an additional poisoning effect which is only evident during operation in a stoichiometric to lean environment, and which cannot be reversed at 500~ We attribute this particular effect to SO2-induced coking of the Pd catalyst in rich conditions: treatment in lean conditions with no sulfur in the feedstream results in significant recovery of activity in the lean A/F ratio region, but not in the rich A/F ratio region. We also found that the presence of SO2 resulted in a slight decrease in the CO conversion and a significant decrease in the NOx conversion in rich conditions, but the coking effect noticed in the HC activity did not significantly affect CO and NOx activity. This observation suggests that the active site participating in the oxidation of propane differs from those sites catalyzing the oxidation of CO and reduction of NO Turning now to the thermally aged 0.13% Pt, 0.0093% Rh production catalyst, we show the HC, CO and NOx conversion efficiencies as a function of mean A/F ratio at 500~ using propylene to represent the hydrocarbon in Figure 11. It is interesting to note that for this catalyst, the effect of adding 30 ppm SO2 is generally similar to the Pd catalyst: the HC and NOx conversion efficiencies were significantly decreased in rich conditions, while the CO conversion efficiency was only moderately decreased, but again in rich conditions. With no sulfur present, it is interesting to note that in lean and stoichiometric conditions, the propylene conversion efficiency was slightly lower for the Pd catalyst in comparison to the Pt-Rh catalyst, while the Pd catalyst was significantly more active than the Pt-Rh catalyst for propylene oxidation in rich conditions, between 14.6 and 14.1 in mean A/F ratio units. This hydrocarbon activity advantage of the Pd over Pt-Rh was completely canceled when 30 ppm SO2 is present in the feedstream, and became a disadvantage when sulfur was removed from the feedstream, as the Pt-Rh catalyst recovered all of its original activity (not shown in the figure), but the Pd catalyst did not. The rapid decrease in HC activity in extreme A/F ratio conditions (between 14.2 and 14.1) and that the presence of sulfur does not sigaaificantly affect the activity in this region. We also note that with 30 ppm SO2 present, the decrease in the NOx activity of the Pt-Rh catalyst was not as large as the decrease in the NOx activity observed with the Pd catalyst. This result is consistent with the reported relative resistance of Rh to direct sulfur poisoning [13].

742 100 80

-0

.

60 40 20 o

~" 1001. ~

o

9

|

,

I

=

*

~

*

-

=

9

=

9

~

*

=

*

"

*

"

9

=

96

"~---O UJ 92 ~ 9

9

i

84

0g

N•

~

14.2

14.4

is

ls.2

Mean A/F Ratio Figure 9. Effect of sulfur dioxide on the activity of thermally aged Pd in a cycled stoichiometric exhaust as a function of mean air~fuel ratio using propylene as a surrogate hydrocarbon. The HC, CO and NOx conversion efficiencies for the thermally aged 0.13% Pt, 0.0093% Rh catalyst as a function of mean air/fuel ratio at 500~ were again determined except that propane was used to represent the hydrocarbon. The result is shown in Figure 12 first with no SO2, then with 30 ppm SO2 in the feedstream. The effect of sulfur on catalyst activity followed a similar trend as with the previous case: the HC and NOx activity was reduced in stoichiometric and rich conditions, although the HC activity was not significantly affected at extreme rich conditions of 14.2 to 14.1 in A/F ratio. The CO conversion

743

efficiency was also similarly affected, being moderately reduced in rich conditions

100 80 60 40

Oppm 0

o

!

~~o~d~-

v

v

9

,~r

ir ...~;.~;.~,~~" ~ . " HC "v

.

.

,~__j~

.

v

.

.

v

.

v"

v

, v

30 ppm :

20 o

100 .~

96

'~1

88

g

84

(D t-O O

80 10r

L_

0 ppmE]o m

0 ppm K~

80 60

NO~ -

40--

m

20 014

14.2

14.4

14.6

14.8

15

15.2

Mean A/F Ratio

Figure 10. Effect of sulfur dioxide on the activity of thermally aged Pd in a cycled stoichiometric exhaust as a function of mean air~fuel ratio using propane as a surrogate hydrocarbon.

9Note that the magnitude of the effect of sulfur on the overall activity of the PtRh catalyst was not as large as the effect on the Pd catalyst, particularly with regard to the HC conversion.

744 100 O p p m ~ ~ 80

..........

_~ .

.c !

60 40-

20O"

~

96

:~

92

8,oo ,.. . ~

80

r,J

80

I

1

'

NOx"

60

014"

14.2

14.4

14.6

14.8

15

15.2

Mean A/F Ratio Figure 11. Effect of sulfur dioxide on the activity of thermally aged Pt-Rh in a cycled stoichiometric exhaust as a function of mean air~fuel ratio using propylene as a surrogate hydrocarbon.

There is one exception in these results using propane relative to those obtained when propylene was used to represent the hydrocarbon: in extremely lean conditions, the HC activity was enhanced by the presence of SO2: this effect has been reported in previous laboratory studies of propane oxidation [26]. We suggested previously that SO2 promotes acid catalysis of propane dehydrogenation, only in this case, the carbonaceous material may be more easily removed from Pt-Rh than from Pd under oxidizing conditions, thus complete oxidation of propane dominates over coking. Other factors, however, may also be

745 responsible for these observations due to a number of differences in the properties of the two catalysts. For example, the dispersion of the Pt-Rh catalyst is generally significantly greater than the Pd catalyst, and it has been shown that highly dispersed noble metals are less likely to be poisoned by coke formation than similar catalysts with lower noble metal dispersion [43]. Certainly, further study is needed to gain a better understanding of this phenomenon. 10 80

,

HC.

30

60 40

30 ppm

20

0 ppm

.

V

>,, r E:

(L)

~ ,.... ~

(O

UJ tO (/)

. i

(D I..

>

tO

O

100

'

.

96 92

~mmr~

30 ppm

84

"

80 100

i

80 "

0 ppm

NOx

i

60 40 20 014

14.2

14.4

14.6

14.8

15

15.2

Mean A/F Ratio Figure 12. Effect of sulfur dioxide on the activity of thermaly aged Pt-Rh in a cycled stoichiometric exhaust as a function of mean air~fuel ratio using propane as a surrogate hydrocarbon.

746 4. SUMMARY

In this work, we have compared the effect of SO 2 on the three-way performance of a commercially prepared, thermally aged Pd three-way catalyst with that of a commercially prepared, thermally aged Pt-Rh three-way catalyst. The results obtained in the present study were generally consistent with previous laboratory studies of commercially prepared Pt-Rh catalysts [26] and model Pd three-way catalysts [36]. We found that an increase in the sulfur content in simulated cycled stoichiometric exhaust resulted in a loss of both lightoff and wanned-up activity. The magnitude of the impact of sulfur on lightoff activity of both Pd and Pt-Rh catalysts was comparable when propylene was used for the hydrocarbon contribution to the exhaust, and larger but still comparable when propane was used to represent the hydrocarbon in exhaust. The Pd catalyst showed generally better lightoff activity than the Pt-Rh catalyst regardless of the sulfur content in the feedstream, but the opposite was valid when propane was used to represent the hydrocarbon. Under wanned-up conditions, the loss of activity for HC, CO and NOx due to the presence of sulfur was greater under slightly rich conditions than under lean conditions for both Pd and Pt-Rh catalysts, while the magnitude of the impact on propylene and NOx activity under wanned-up stoichiometrie conditions was significant greater for the Pd catalyst than for the Pt-Rh catalyst. When propane was used to represent the hydrocarbons in exhaust, the impact of sulfur on the HC conversion was comparable for both catalysts, although the impact on CO and NOx was greater for Pd than for Pt-Rh. Finally, we found that when propylene was used for the hydrocarbon, the effect of SO2 on the activity of the Pd catalyst was partly irreversible under the conditions used in this study, while the effect on Pt-Rh was completely reversible. When propane was used to represent the hydrocarbon, the effect on the activity of both catalysts was partly irreversible, but the magnitude of the irreversible poisoning was larger on Pd. Part of the irreversible poisoning effect is attributed to a direct interaction or reaction between SO2 and Pd, while the other part is attributed to the promotional effect of SO2 in hydrocarbon coking of the catalyst when alkane hydrocarbons are present. 5.ACKNOWLEDGMENT The authors wish to acknowledge the assistance of Galen Fisher and David Monroe for helpful discussion and comments, and to Doug Ball of the AC Rochester Division for their discussion and assistance with this study.

747 REFERENCES

9

10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25

K. C. Taylor, Ind. Eng. Chem., Prod. Res. Dev. 15 (1976) 264. J. C. Summer, Env. Sci. Tech. 13 (1979) 321. H. C. Yao and J. Yu, J. Catal. 36 (1975) 266. J. C. Summers and K. Baron, J. Catal. 53 (1979)380. W. B. Williamson, H. S. Gandhi, M. E. Heyde and G. A. Zawacki, SAE Paper No. 790942, 1979. G. J. Joy, G. R. Lester and F. S. Molinaro, SAE Paper No. 790943, 1979. J. C. Schlatter and P. J. Mitchell, Ind. Eng. Chem., Prod. Res. Dev. 19 (1980) 288. U. Kohler and H.W. Wassmuth, Surf. Sci. 126 (1983) 448, and references therein. O. K. T. Wu and R. P. Bums, Surf. Int. Anal. 3 (1981) 29. M. L. Burke and R. J. Madix, Surf. Sci. 194 (1988) 223. R. C. Ku and P. Wynblatt, Appl. Surf. Sci. 8 (1981) 250. St. Astegger and E. Bechtold, Surf. Sci. 122 (1982) 491. D. D. Beck, M. H. Krueger and D. R. Monroe, SAE Paper No. 910844, 1991. R. L. Furey and D. R. Monroe, SAE Paper No. 811228, 1981. "Effects of Fuel Sulfur Levels on Mass Exhaust Emissions", Auto/Oil Air Quality Improvement Research Program, Technical Bulletin No. 2, February 1991. A. F. Diwell, C. Hallett and J. R. Taylor, SAE Paper No. 872163, 1987. A. V. Deo, I. G. Dalla Lana and H. W. Habgood, J. Catal. 21 (1971) 2710. A. Datta, R. G. Cavell, R. M. Tower and Z. M. George, J. Phys. Chem. 89 (1985) 443. H. G. Henke, J. J. White and G. W. Denison, SAE Paper No. 872134, 1987. E. S. Lox, B. H. Engler and E. Koberstein, SAE Paper No. 890795, 1989. J. C. Dettling, H. S. Hwang, S. Pudick and S. J. Tauster, SAE Paper No. 900506, 1990. M. A. Harkonen, S. Salamae, T. -K. Rantakyla and V. J. Pohjola, SAE Paper No. 900498, 1990. J. S. Rieck, W. Suarez and J. E. Kubsh, SAE Paper No. 892095, 1989. "Effects of Fuel Sulfur on Mass Exhaust Emissions, Air Toxins, and Reactivity",Auto/Oil Air Quality Improvement Research Program, Technical Bulletin No. 8, 1992. J. C. Summers, J. F. Skowron and W. B. Williamson, SAE Paper No. 920558, 1992.

748 26

D. R. Monroe, M. H. Krueger, D. D. Beck and M. J. D'Aniello, Jr., "the Effect of Sulfur on Three-Way Catalysts", in Catalysis and Automotive Pollution Control 11, A. Crucq, ed., Amsterdam: Elsevier Science Publishers, 1991. 27 J. C. Summers, J. J. White and W. B. Williamson, SAE Paper No. 890794, 1989. 28 G. B. Fisher, M. G. Zammit and W. J. LaBarge, SAE Paper No. 920846, 1992. 29 J. C. Dettling and Y.-K. Lui, SAE Paper No. 920094, 1992. 30 H. Muraki, SAE Paper No. 910842, 1991. 31 T. Yamada, K. Kayano and M. Funabiki, SAE Paper No. 930253, 1993. 32 J. C. Summers, J. F. Skowron and M. J. Miller, SAE Paper No. 930386, 1993. 33 R. A. Giacomazzi and M. F. Homfeld, SAE Paper No. 730595, 1973. 34 G. L. Barnes and R. L. Klimisch, SAE Paper No. 730595, 1973. 35 D. D. Beck, J. W. Sommers and C. L. DiMaggio, Appl. Catal. B: Env., 3 (1994) 205. 36 S. Subramanian, R. J. Kudla, C. R. Peters and M. S. Chattha, Catal. Lett. 16 (1992) 323. 37 D. D. Beck, D. R. Monroe, C. L. DiMaggio and J. W. Sommers, SAE Paper No. 930084, 1993. 38 D. D. Beck, M. H. Krueger, D. R. Monroe, D. J. Upton, J. M. Lendway and D. R. Smith, SAE Paper No. 920099. 39 C. L. DiMaggio and D. D. Beck, manuscript in preparation. 40 S. M. Davis and G. A. Somorjai, Chem. Phys. Solid Surf. 217 (1982). 41 E.E. Wolf and F. Alfani, Catal. Rev. Sci. Eng. 24 (1982) 329. 42 J. Barbier and P. Marecot, J. Catal. 102 (1986) 21. G. A. Olah, G. K. S. Williams, J. D. Field, and D. Wade, "Hydrocarbon Chemistry", Wiley, New York, 1987. 43 H. Wise, J. McCarty, and J. Oudar, in "Deactivation and Poisoning of Catalysts", J. Oudar and H. Wise, eds., Marcel Dekker, New York, 1985.


749

AN X-RAY ABSORPTION SPECTROSCOPIC INVESTIGATION OF AGED AUTOMOTIVE CATALYSTS

F. Mairea, M. Capelleb, G. Meunierb, J.F. Beziaub, D. Bazina, H. Dexperta, F. Garinc, J.L. Schmitte and G. Mairec

aLURE, bdt. 209D, Paris Sud, 91405 Orsay-cedex bpSA, Centre Technique de Belchamp, 25420 Voujeaucourt et PSA Etudes et Recherches, 78140 Vdlizy-Villacoublay cLERCSI, URA1498, CNRS-ULP-EHICS, 4 rue Blaise Pascal, 67070 Strasbourg, France

ABSTRACT

By XAS investigations of model and automotive catalysts (Pt, Rh / CeO2 / A1203) associated with analytical electron microscopy, it is shown that for both model and aged catalysts treated in air at high temperatures, true alloyed phases were formed. Despite sintering of the alloyed aggregates, the ECE Test Procedure indicated that the commercial aged catalysts were still active and gave emissions below the standard limits.


A bimetallic catalyst system of industrial importance presently is the threeway catalyst (T.W.C.) used for the simultaneous conversion of carbon monoxide, hydrocarbons,and nitrogen oxides in automobile exhaust. Typical commercial T.W.C.'s contain platinum and rhodium associated with ceria and alumina. Platinum is an effective catalyst for the oxidation of CO and "HC". However, for the reduction of nitric oxide this metal is less effective [1,2]. Rhodium is the essential element in the T.W.C. for the conversion of NO into N2. Ceria promotes platinum and rhodium by preventing sintering of the catalyst particles, increasing the dispersion of the catalyst [3], providing oxygen storage by shifting between

750 Ce203 and CeO 2 when passing from fuel-rich to fuel lean conditions [4], by enhancing the water-gas shift reaction [5,6], and stabilizing the alumina support [7].During ageing the T.W.C. displays a general loss of activity. The thermally induced sintering due to elevated temperatures, and various compositions of the exhaust gas, results in the support sintering and modifications (A1203, CeO2) , in the noble metal particles coalescence or migration of oxides on the surface or in the bulk in oxidative conditions [8,9,10]. Deactivation may also occur via chemically induced poisoning, which affects active metal sites due to strong deposition or chemisorption of contaminants on the catalyst such as P, S, Pb, Zn, Ca, Si, etc. [11]. Here too, the temperature and composition of the exhaust gas affect the degree of deactivation. Over the last decade, several investigations of the deactivation processes were dedicated to the studies of noble metal particles present in "in-use" catalysts. Some studies indicate that the particles are clearly bimetallic and not separate clusters of Rh and Pt [12]. Reports of beneficial synergistic reactivity of Pt-Rh bimetallics toward catalyzing automotive exhaust reactions has motivated further research involving Ptx-Rhl_x alloys [ 13]. Studies on model surfaces of PtRh alloys (single crystals) confirmed synergies for different reactions [14,15]. The major investigations published on aged automotive catalysts were obtained for metals deposited on AI203 in the abscence of CeO2, or with simple laboratory feedstreams and accelerated catalyst ageing schedules [13,16]. Extrapolation of results obtained from laboratory reactor experiments to the actual exhaust environment should be done with caution. Commercial T.W.C.'s contain significant amounts of CeO 2. In addition to the Pt-Rh interactions, the interactions between base metal additives and the noble metals can play an important role in determining the performance and durability of T.W.C.'s. To understand the general loss of activity during ageing of automotive exhaust catalysts we used X-Ray Absorption Spectroscopy (XANES and EXAFS) allowing "in-situ" measurements to characterize flesh and vehicle-aged commercial catalysts. Complementary techniques were necessary 9XRD, TEM, STEM, XPS in association with catalytic tests performed in a laboratory reactor working under transient conditions [16], along with various cycles done at Belchamp (PSA) under more realistic conditions. We already have made preliminary investigations by X-Ray Absorption Spectroscopy on model catalysts with high loadings of Pt and Rh/A1203, treated under elevated temperatures and various compositions of gases, showing major changes in microstructure and microchemistry" increasing particle size, presence of bimetallics or alloys, interactions between Pt, Rh and CeO2 or A1203, catalytic deactivation [17, 18]. We present in this paper results obtained for vehicle-aged, commercial

751 automotive exhaust catalysts which have been studied using the aforementioned techniques. 2. EXPERIMENTAL

2.1. catalysts Two sets of catalysts were selected for this study, "model" catalysts with high contents of noble metals supported on alumina (already discussed in reference 17) and the "commercial" catalysts furnished by PSA containing Pt, Rh and CeO2 / A1203 (fresh and aged). Model catalysts: Four supported catalysts were employed : (a) 1%Rh/y-Al203 calcined in air at 600~ (b) 10%Pt/7-AI203 reduced at 300~ in H 2, (c) 5%Pt-l%Rh/7-A1203 calcined in air at 600~ (d) 5%Pt-l%Rh/ y-Al203 calcined in air at 1600~ The catalysts were prepared by co-impregnation of 7-alumina from Jolmson Matthey with solutions of platinum sponge dissolved in HC1 and of RhC13 in H20. Calcination at 600~ did not affect greatly the structure of 7-A120 3 despite sintering, whereas at 1600~ in air the A1203 was exclusively of the alpha type as detennined by XRD. Commercial formulations: These catalysts contained Pt and Rh supported on alumina deposited in monoliths which also contained ceria. The two vehicle-aged samples A 2 and B 2 were collected after 65,000 and 103,000 customer-operated kilometers respectively, both aged catalysts contained approximately equivalent amounts of precious metals and contaminants, as listed

Table 1"Characterization data (in wt. %)for fresh and aged catalysts Catalyst

Pt

Rh

Ce

P

S

Pb

Zn

9

0.70 0.72

0.16 0.13

16.3 7.6

0.01 0.82

0.05 0.14

0.05 0.29

0.02 0.32

40 13

0.60 0.68

0.12 0.13

13.7 12.7

0.01 1.19

0.03 0.17

0.01 0.17

0.02 0.37

gw~ific area

m2/g BET A1 Fresh A2 Aged (103,000

km) B 1 Fresh B2 Aged (65,000 km)

752 in Table 1, data for the fresh catalysts A 1 and B1 are included for comparison. The powders, A 1, A 2, B1, B2, were extracted from monoliths using an "ad-hoc" tool to scratch the channels of the monoliths. The amount of catalyst needed for XAS analysis were 800 mg for the transmission mode and 2000 mg for the fluorescence mode. The samples A1, A 2 and B 1, B 2 were not obtained from the same monolith. The main difference concerned the aged A2 sample having a much lower content of Ce due to erosion of the wash-coat at the entrance of the monolith. The ECE Test Procedure indicated that both A 2 and B 2 aged catalysts were still active and trader the standard limits.

2.2 X-Ray Absorption Spectroscopy (XANES and EXAFS) X-Ray Absorption Spectroscopy is a technique in which the ejected photoelectron acts as a probe of the surrounding environment in a manner similar to electron scattering. Since the absorption edges of different elements are well separated in energy (which is the case for the LII I Pt edge (11,564 eV) and the K Rh edge (23,220 eV)) the teclmique is element specific and able to examine the surroundings of Rh or Pt in the presence of the support [19,20]. We used X-Ray Absorption Spectroscopy combining X-Ray absorption near edge structure (XANES) and extended X-Ray absorption fine structure (EXAFS) to extensively characterize our fresh and aged commercial catalysts. XANES is sensitive to the electronic data (oxidation state) and EXAFS data can provide information on bond distances, coordination numbers, disorder, and types of ligand for the first few coordination spheres [21 ]. We used the synchrotron radiation facilities of LURE (ORSAY) from the DCI storage ring running at 1.85 GeV with an average current of 250 mA. The XAS data (XANES and EXAFS) were collected on the EXAFS-4 station using a conventional step-by-step set up with a channel cut mono-chromator Si (111) for Pt and Si (311) for Rh and two ion chambers as detectors. In this work, all X-Ray absorption spectra were obtained at 25~ with the transmission detection configuration. Consequently all the catalysts listed above were studied at the LII I Pt edge but only the model catalysts were studied at the K Rh edge. The EXAFS spectra were analyzed in a conventional manner [22]. The amplitude and phase shift parameters associated with the backscattering process were extracted from reference compounds : Pt mid Rh polycrystalline foils ; PtO2 ; Rh203 ; RhC13,nH20 ; H2PtC16,6H20. The structural parameters associated with each shell in the reference compounds were obtained from crystallographic data. For consistency, the phase and amplitude functions obtained from the reference compounds were compared with those generated by Mc Kale et al. [23] using curved wave models for scatterers of the same identity.

753 We measured the variation of eri namely the Debye-Waller factor, arising from both static and dynamic disorder, compared to its value in the standard. Finally, we used a two-shell least-squares fitting procedure to extract the values of Nj(coordination numbers), Rj(bond distances) and At~i. The photoelectron mean free path F has been fixed to its value in the standard. The XAS spectra recorded with the commercial formulations correspond to an averaging along the length of the monolith.

2.3. Analytical electron microscopy Only the commercial formulations, fresh and aged, respectively A1, B1 and A2, B 2 have been characterized. For the TEM measurements, ethanol was added to a few finely ground grains of the catalyst and the resultant suspension sonicated in an ultrasound bath before deposition of a few drops on a 200 mesh copper grid coated with a holey carbon film. Bright field micrographs were recorded at accelerating voltages of 200 kV using a JEOL 2010 insmnnent equipped with a spectrometer for energy dispersion Z-MAX from TRACOR (available at the I.F.P. in Rueil-Malmaison) to differentiate Pt, Rh, Pt/Rh aggregates from CeO2, to determine the ratio Pt/Rh in the bimetallies and to localize other oxides (eg. Ba, Zr, La). Metallic particles are not visualized under 7 A.

3. RESULTS The results from different techniques will be presented in the following sections and then discussed together 3.1 XAS ANALYSIS Two kinds of information were extracted from the data. Qualitative information is gained from the change in the white line intensity. Quantitative results are extracted from the EXAFS analysis, and a common way to visualize the change of the metal environment when comparing different catalysts is to plot the magnitude of the Fourier transform (FFT) of the EXAFS oscillations. For the supported model catalysts studied it resulted that for all catalysts treated in air at 600 ~ only well dispersed oxidic phases were observed on the LIII edge of Pt and the K edge of Rh as illustrated in Figure 1 for the 5%Pt]A1203, 1%Rh]A1203 and the 5%Pt-l%Rh/A1203 catalysts treated in air at 600 ~ [17,18]. The Fourier transform curves are compared with the references PtO2 and Rh203. It appears that the contributions of the second and third shells are very weak compared to bulk PtO2 or Rh203 in agreement with the recent work of Beck et al. [24] for Rh/A1203 catalysts after treatment in high temperature oxidizing environments. The 5%Pt-1%Rh/7-A1203 catalyst treated in air at 1600 ~ reveals the formation

754 of an alloy Pt51Rh49 with a mean particle size _ r = =

.=

e~

r f

J

r

o

0.00

7

20.00

10.8

40.00

0.00

DISTANCE ~ x 10-1

5.9

5%Pt-1%Rh / Ai20 3

x

air 600~

"o

20.00

40.00

DISTANCE /~ x 10-1 5%Pt-1%Rh / A120 3 air 1600~

..,= =1

r "O

0.00

20.00

40.00

DISTANCE /~ x 10-1

0.00

20.00 40.00 D I S T A N C E /~ x 10 -1

Figure 1 Model catalysts : different FFT moduli are shown. Curve (1) corresponds to the 5%Pt/A120 3 treated m air at 600 ~ (Pt LIII edge). Curve (2) to bulk Pt02. Curve (3) to the l%Rh/Al20 3 treated m air at 600 ~ (Rh K edge). Curve (4) to Rh20 3. Curve (5) to the 5%Pt-l%Rh/A120 3 treated m air at 1600 ~ (Pt L iIiedge).

metal, Rh203,

l%Rh/7-A1203 and two model catalysts. The 5%Pt-l%Rh/?A1203 catalyst treated in air at 600~ is constituted of PtOx and RhOx entities only.

756 15.00

, (~)

,

.

,,,-

--

.

.

.

.

.

(2)

=:

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,.o

.
99.99%) was passed through a carbonyl trap. The helium feed to the reactor was purified by passing it through an oxygen trap and also through a silica-gel trap at liquid nitrogen temperature. H2 (>99.999%) was further purified with a hydrocarbon filter. The apparatus shown in Fig. 1 and procedure listed above represent only a slight departure from the method first described by Komai et al. [4]. The main differences are:

793

CO Methanation Apparatus H2 I 02 ~ ' - I ~

CO [ ~ ~

.el

i

FIB

i lI Furnace

Column Haysep N

Air

H2

Figure 1. Schematic diagram of the apparatus. 1) the samples are oxidized in a flow of 0 2 for 30 minutes instead of 1 hour at 400~ 2) the samples are reduced in a flow of H 2 for 30 minutes instead of 1 hour at 400~ and 3) 2 pulses of CO (2 cm 3 each) are used instead of a single large dose. Whereas Komai et al. used the technique only for Pt on alumina catalysts, we have extended it to Pd and Rh containing catalysts. Preliminary experiments, carried out with single-component Pd/A120 3 and Rh/ A120 3 confirmed that reaction under the conditions outlined above is sufficient to convert all of the adsorbed CO to CH4. Moreover, we have found that Pd- containing catalysts require a modified procedure from that used for the Pt based catalysts. In other studies carried out in parallel with this study, we have found that even relatively mild reducing conditions (ca. 300~ or higher) cause significant sintering of Pd particles, particularly in flesh catalysts with relatively high initial dispersions. Others have reported similar observations [11]. In addition, Pd-containing

794 catalysts cannot be exposed to H 2 below 70~ without forming Pd hydride [12]. Consequently, we used 150~ as the standard temperature for reducing the Pd/Rh catalyst. Thus, after 400~ oxidation for 30 min, the palladium catalysts were cooled to 150 ~ in flowing 02 (40 cm3/min) and then reduced at 150~ in H 2 for 30 min followed by a He purge at 150~ for 30 min.

2.3 X-ray diffraction (XRD): XRD patterns were recorded on a Philips X-ray generator with a DebyeScherrer camera. CuKot X-rays (k = 1.5418 A) were used as the X-ray source. XRD measurements were performed on powdered washcoat scraped from the comer region of exposed channels on the outer surface of the cores. The XRD apparatus used to analyze the samples have been described in detail previously [8]. Particle sizes were estimated using the Scherrer equation with correction for instrumental line broadening. 3. RESULTS Table 1 compares our results obtained for the EuroPt-1 catalyst using the CO methanation technique with results reported by other groups [13-17] using xray diffraction, conventional chemisorption, and TEM. A dispersion of 45% was calculated using the spherical particle approximation and an assumed adsorption stoichiometry of 1 CO molecule per exposed Pt atom. If the adsorption stoichiometry is instead assumed to be 0.7, in keeping with previous studies of CO chemisorption out on Pt catalysts [17,18], then the dispersion becomes 65% in close agreement with the studies shown in Table 1 employing other techniques. The results obtained for the flesh and aged commercial PffRh and Pd/Rh TWCs are shown in Table 2. The first column contains the dispersions and calculated spherical particle sizes (in parentheses) derived from the CO methanation technique based on an assumed adsorption stoichiometry of 1 CO per exposed noble metal atom. The arbitrary choice of a stoichiometric factor of 1, rather than the value of 0.7 suggested by the EuroPt-1 catalyst, was made on the basis of several factors. The main reason is that the presence of Rh in these catalysts (16% and 10% of the noble metal weight in the Pt/Rh and Pd/Rh catalysts, respectively) is likely to increase the average stoichiometric factor above 0.7 due to the presence of gem-dicarbonyl species on Rh. Bimetallic Pt/Rh particles have been fotmd in automotive catalysts, sometimes with surface enrichment by Rh [20,21] or even bulk enrichment of selected particles as

795 evidenced by TEM [9]. Thus the Rh in automotive TWCs may affect the adsorption stoichiometry much more strongly than the overall loading ratio would suggest. With the assumed stoichiometric factor of 1, the dispersion of the PtlRh TWC went from about 57% in the flesh state to about 13% after vehicle aging, corresponding to a growth in particle size from 16+1 A to 72+6 A. The Pd/Rh catalyst started out at about 42% dispersion and decreased to 2.4% dispersion atter vehicle aging. This corresponds to a growth in particle size from 21+2 A to 366+46 A assuming spherical particles. Table 1.: Chemisorption, XR , and TEM results o f EuroPt-1.

Method

Dispersion (%)

Ref.

XRD TEM 02 adsorption H 2 adsorption CO-H 2 titration

65 56-66 50-62 65 45 (65)a

[13] [14] [ 15] [ 16] This study

a Assuming CO:Pt=0.7 Column 2 of Table 2 shows the dispersion values which we measured previously using conventional volumetric adsorption techniques. For the PtlRh catalyst, where it was necessary to use H 2 as the probe molecule due to a strong and irreversible interaction of CO with one of the washcoat components (not present in the Pd/Rh catalyst), the volumetric chemisorption data agree fairly well with the CO-H 2 methanation technique. However, for the Pd/Rh catalyst, the volumetric chemisorption method employing CO gave a nonsensical dispersion of 174% for the flesh catalyst and an implausible dispersion of 96% for the vehicleaged catalyst. Column 3 of Table 2 lists the apparent particle sizes obtained from x-ray diffraction. For both the Pt/Rh and Pd/Rh catalysts, particles were too small to detect with our x-ray system. The vehicle aged Pt/Rh catalyst gave a particle size of 110+20 A, in good agreement with both the CO-H 2 methanation and volumetric chemisorption results, particularly considering that only the particles greater than about 40/k contribute to the x-ray data. Similarly, the XRD particle

796 size of the aged Pd/Rh catalyst (470+120 A) is consistent with the particle size of 366+44 A. obtained with the CO-H 2 titration technique.

Table 2.: Chemisorption andXRD results of commercial TWC catalysts. Dispersion,

% (Particle size, A)a XRD

Sample CO-H 2

Volumetric

Methanationbchemisorption c Pt-Rh fresh Pt-Rh vehicle aged Pd-Rh fresh Pd-Rh vehicle aged

56.6 (16+ 1) 12.7 (72+6) 41.9 (21+2) 2.4 (366+44)

73 (12) 8 (114) 174 (--) 96 (--)

n.d.d 110+20 n.d.d 470+120

a Particle size estimated assuming spherical particles. b Assuming 1 CO per noble metal surface atom. c From Ref.[8], assuming 1 CO or 1 H per noble metal surface atom. d Not detected; below detectable limit (< 40 b). Note: Error band in CO-H2 methanation particle sizes based on range of values obtained in repeat experiments. Typically 5-6 runs were made on each sample. Error bands in the XRD particle sizes result from particle size estimates made from different x-ray lines.

4. DISCUSSION

Table 2 clearly shows that of the three techniques compared (CO methanation, volumetric chemisorption, and XRD) only the CO methanation technique yielded a complete set of realistic dispersion/particle-size data for all four of the flesh and aged commercial catalyst samples analyzed. Volumetric chemisorption was very difficult to perform on these samples because of interferences from the metal oxide components of the catalyst, while XRD was limited by its inability to detect small particles with our conventional source and detector. The CO methanation technique is relatively fast (less than two hours for

797 a complete test) and requires only standard equipment found in most catalysis laboratories. (Even though we used a GC, the analysis can be carried out using a standard total hydrocarbon analyzer equipped with a flame ionization detector.) The high sensitivity of the technique is clearly evident in its ability to easily measure CO uptakes (i.e. CH4 yields) on the 0.46 wt% Pd/Rh catalyst which was only slightly more than 2% dispersed. In contrast, the 65% dispersed 6.3 wt% EuroPt-1 catalyst presented the greatest challenge with the CO methanation technique; the methane yield was so high that the catalyst charge had to be decreased to 3 mg to avoid overloading the GC column. Another indication of the sensitivity of the CO methanation technique is that even highly sintered catalysts only required about 100 mg of sample versus sample sizes near 10 g required in pulse CO chemisorption studies of automotive catalysts by Dalla Betta et al. [ 10]. Aside from the high sensitivity of the CO methanation technique, its most attractive feature for the analysis of complex automotive catalysts is the apparent absence of complications due to adsorption of CO on sites other than noble metal sites. One possible explanation raised by Bozon-Verduraz et al. [22] is that any CO which interacts strongly with basic washcoat components such as ceria, lanthana and baria to form stable compounds such as carbonates, does not get counted because it does not react with hydrogen to form methane. On the other hand, any CO which adsorbs weakly on the support will get counted, because it will desorb during heating, re-adsorb on the noble metal particles, and react with H2 to form methane. Apparently, the techniques employed in the CO-methanation experiment, namely quick dosing of CO from flowing pulses and purging of the reactor cell with flowing H 2 atter CO dosing, prevent significant accumulation of weakly adsorbed CO on non-noble metal washcoat components. In this respect, the CO methanation technique closely resembles pulse adsorption methods, as noted in a follow-up study to the original work by Komai et al. employing the same set of Pt/A1203 catalysts [23]. IR spectroscopy was used in the follow-up study to confirm the absence of CO on the support following the H 2 purge step. In the early days of automotive catalysis, the oxidation catalysts had washcoats consisting essentially only of ~/m1203. Thus the catalyst formulations were simple enough that the measurement of metal surface areas, although laborious [10], could be performed. With the advent of complex washcoats in TWCs, post mortem analyses of field-aged automotive catalysts have relied largely on BET surface area measurements as a probe of the extent of thermal damage. As noted in our previous study, however, BET measurements are useful only for identifying catalyst which have suffered gross thermal abuses, usually from engine misfires. In the case of the Pt/Rh and Pd/Rh catalysts examined here, BET surface areas were very close to fresh catalyst levels, indicating the absence of severe thermal

798

damage. Nevertheless, it is clear from the CO methanation data that thermal damage far short of that required to cause significant phase change in the alumina support can lead to dramatic decreases in noble metal surface areas (and dispersions). Although XRD and TEM have been employed for in-depth analysis of selected catalysts [9,21], very little chemisorption data have been published for field-aged automotive catalysts [10]. The chemisorption technique based on CO methanation opens the door to in-depth noble metal particle size characterization of large numbers of field aged catalysts. We are currently in the process of doing this on a series of catalysts with well documented thermal histories, with the eventual goal of establishing a quantitative link between noble metal particle size and catalytic activity. We are also continuing our characterization studies of the two COlmnercial catalysts employed in the present study, using HRTEM to obtain a complete particle size distribution. Preliminary indications are that the particle size distribution is broad in field-aged catalysts; consequently the spherical particle assumption normally used to estimate particle sizes from chemisorption data is not particularly meaningfid. Rather than estimate a particle size from chemisorption data and compare it with a particle size histogrmn from HRTEM, our preliminary results suggest that a more meaningfid correlation can be obtained by measuring the total noble metal surface area in chemisorption and comparing it to the total noble metal surface area obtained by calculating and summing the surface areas of individual particles in the HRTEM particle size histogram.

5. SUMMARY

A chemisorption teclmique developed by Komai et al., based on CO methanation, was successfully used to analyze noble metal dispersions of both fresh and vehicle-aged P t ~ l and Pd/Rh commercial automotive three-way catalysts. The teclmique is relatively rapid (< 2 hours), extremely sensitive, and largely free from complications due to adsorption of CO on non-noble metal componems of the washcoat (support, promoters, stabilizers, etc.). Particle sizes of the vehicle-aged catalysts, calculated by applying the spherical particle assumption to the dispersions measured by the CO methmlation method, agreed well with particle sizes calculated from x-ray diffraction line-broadening data. These results indicate that the CO methanation teclmique can be applied routinely to obtain fast and accurate measurements of noble metal surface areas in automotive catalysts retrieved from the field, even those with metal dispersions ca. 2% or less.

799 ACKNOWLEDGMENT

We gratefully acknowledge Prof. A. Frelmet for his help in obtaining the sample of EuroPt-1. The authors also acknowledge the assistance of the late C. R. Peters in providing the x-ray diffraction data. REFERENCES

J.R. Anderson, "Stlx~cture of Metallic Catalysts," Academic Press, New York, NY, 1975. T.R. Hughes, R.J. Houston, and R.P. Sieg, Ind. Eng. Chem., Proc. Design and Dev.,1 (1962) 336. J.E. Benson and M. Boudart, J. Catal., 4 (1965) 704. S. Komai, T. Hattori, and Y. Murakami, J. Catal. 120 (1989), 370. J.B. Cohen, Ultramicroscopy, 34 (1990) 41. L. Spenadel and M. Boudart, J. Phys. Chem., 64 (1952) 204. J. Prasad, K.R. Murthy, and P.G. Menon, J. Catal., 52 (1978) 515. R.K. Usmen, R.W. McCabe, G.W. Grahaln, W.H. Weber, C.R. Peters, and H.S. Gandhi, SAE paper 922336 (1992). J.-O. Malta and J.-O. Bovin, Microscopy, Microanalysis, Microstructures, 1 (1990) 387. 10 R.D. Dalla Betta, R.C. McCune, and J.W. Sprys, Ind. Eng. Chem., Prod. Res. Dev.,15 (1976) 169. 11 J.J.F. Scholten and A. Van Montfoort, J. Catal., 1 (1962) 85. 12 P.C. Aben, J. Catal., 10 (1968) 224. 13 V. Gnutzmalm and W. Vogel, J. Phys. Chem., 94 (1990) 4991. 14 J.W. Geus and P.B. Wells, Appl. Catal., 18 (1985) 231. 15 P.B. Wells, Appl. Catal., 18 (1985) 259. 16 A. Fremlet and P.B. Wells, Appl. Catal., 18 (1985) 243. 17 K. Kunimori, T. Uchijilna, M. Yalnada, H. Matsulnoto, T. Hattori, and Y. Murakalni, Appl. Catal., 4 (1982) 67. 18 J.E. Benson, H.S. Hwang, and M. Boudart, J. Catal., 30 (1973) 146. 19 W.B. Williamson, H.S. Gandhi, P. Wynblatt, T.J. Truex, and R.C. Ku, AIChE Symposium Series, 76 (1980) 212. 20 F. Bozon-Verduraz, D. Tessier, and A. Rakai, J. Catal., 127 (1991) 457. 21 B.R. Powell and Y.L. Chen, Appl. Catal., 53 (1989) 233. 22 T. Hattori, S. Komai, E. Nagata, and Y. Murakalni, J. Catal. 127 (1991), 460.




801

EFFECTS OF SINTERING AND OF ADDITIVES ON THE OXYGEN STORAGE CAPACITY OF PtRh CATALYSTS.

D. Martin, R.Taha and D. Duprez Laboratoire de Catalyse en Chimie Organique, URA 350 CNRS 40 Av. du Recteur Pineau, 86022 Poitiers Cedex, France

ABSTRACT : PtRh/A1203 and PtRh/CeO2-AI203 bimetallic catalysts (Pt+Rh = 60 lamolg-1) were prepared via chlorine-free precursors. Oxygen storage capacities (OSC) were measured on the fresh (calc. 723K) and on the sintered catalysts (1%O2 + 10%H20, 2h, 973K and 1173K). On alumina catalysts, only Rh can promote OSC which is extremely sensitive to sintering. OSC values are higher on alumina-ceria catalysts, but do not depend on the composition of the bimetallics. Moreover ceria renders the catalysts resistant to sintering. PtRh/A1203 and PtRh/CeO2-Al203 were modified by C1, SO42- and K. On A1203, OSC variations due to the additives follow the same trend as the variations of oxygen mobility (deduced from 180/160 isotopic exchange). Chlorine and sulfur are inhibitors of OSC while K, at low content, is a promotor.

1. INTRODUCTION

Rare earth oxides, especially cerium oxide, are used to improve the oxygen storage capacity (OSC) of three-way catalysts. Noble metals, in particular rhodium, play ml active role in promoting the OSC of the support [1-5]. The mechanism of OSC can be described in terms of three principal steps : - dissociative adsorption and desorption of molecular oxygen on the metals - transfer of active oxygen species from the metal to the support and surface migration of these species on the support - storage of oxygen by cerium oxide.

802 Duprez m~d al. investigated the first and the second step by means of 160/180 isotopic exchange [6-8]. The rate of step 1 can be deduced from the rate of the 1602/1802 equilibration reaction that occurs on the metal : 1802(gas) + 1602(gas) ~

2 18O160(gas )

(1)

while the rate of step 2 is in direct relation with the rate of isotopic exchange of 1802 with the 160 of the support 9 1802(gas) + 160(sup.) -+ 180160(gas) + 180(sup.)

(2)

The surface of ceria being readily reduced at low temperature (< 473K) in the presence of noble metals [1,4], step 3 is expected to be very rapid under the usual conditions of exhaust gas catalysis (T=673-773K). Duprez and Kacimi [7] showed that rhodiuln was the metal which has the highest intrinsic rate in reaction (1). Accordingly the rate determining step (rds) of the mechanism of OSC oll rhodium should be the transfer and the migration of oxygen at the surface of the support. Our aim, in the first part of this paper, is to study the effect of the sintering of PtRh/A1203 and PtRh/CeO2-A1203 catalysts on the OSC and to correlate the OSC with the surface migration of oxygen measured by 1802(gas)/160(support) isotopic exchange [6,8]. In the second part of this paper, we study the effects of certain additives (SO42-, C1) on the OSC values and on the oxygen mobility in the catalysts. As we have shown recently that the surface mobility of oxygen was linked to the basicity of oxides used as supports [8], we have also investigated the effect of potassium. 2. EXPERIMENTAL The support was a y-A1203 (100 m2g -1) supplied by IFP. A 12wt.% CeO2A1203 support was prepared by impregnating the 7-A1203 with aqueous solutions of ceric alnmonium nitrate. The catalysts used in the sintering studies were prepared by successive impregnations with aqueous solutions of dinitrodiamlnine platinum(II) and of rhodium(III) nitrate. After impregnation, the catalysts were dried and calcined at 723K (flesh catalysts). They are referred to here as PtRhXA

803 and PtRhXCA, where A desigamtes alumina, CA, ceria-alumina and X is the atomic percentage of rhodium : % (Rh / Pt+Rh). Aliquot samples of each catalyst were sintered for 2 h at 973K and at 1173K under a continuous flow of 1%02 + 10%H20 (vol%) in nitrogen. In the second phase of the experiments (effect of additives), Rh catalysts prepared on two different supports 9y-A1203 (100 m2g "1, IFP), CeO2/y-AI203 (93 m2g-1, on IFP by impregnating a hydrochloric acid dried and calcined

alumina) were used. All the modified catalysts were prepared fresh catalyst with aqueous solutions of dimnmonium sulfate, or potassium nitrate. After modification, the catalysts were at 723K. They are referred to here as RhSyP, where y is the

weight percentage of the additive P (P=SO42-, C1 or K) and S is for the type of support (S=A for alumina and CA for ceria-alumina). The weight percentages of rhodium are 0.51 for catalysts supported on alumina and 0.53 on ceria-alumina. Dispersion measurements were carried out on fresh catalysts in a pulse chromatographic system previously described [9,10]. The catalysts were reduced at 723K in H2 degassed in Ar (impurities < l ppm) and cooled down to room temperature. Hydrogen chemisorption (HE), oxygen (OT) and hydrogen (HT) titrations were successively recorded. Metal dispersion was deduced from oxygen titration of the chelnisorbed hydrogen using the following stoichiometries 9H/Rhs =1, O/Rhs = 1.5 and H/Pts = O/Pts = 1. OSC and OSCC (Oxygen Storage Capacity Complete) measurements were carried out in a pulse chromatographic system. The catalyst sample (10 to 50 mg) was inserted in a U-quartz reactor, heated to 723K (4 Kmin-1) in a helium flow (30cm3min-1 ; less than 1 ppm impurities) and then oxidized to saturation by 02 pulses (0.268 cln 3) injected every other minute ("oxygen storage"). The CO pulses were then injected, at TOSC (423K< TOSC 5 nm in size). However, bearing in mind the greater complexity of STEM when compared with CTEM, the number of crystallites examined by this teclmique remained fewer (1569 particles measured using CTEM, against 100 particles measured and analyzed using STEM). STEM analysis shows that three particle populations exist: Pt, Pt-Rh and CeO2-Fe203 (Table 2). It also shows that aging results in an enrichment in Rh of the mixed Pt-Rh particles at the expense of the particles of Rh, which exist in a hyperdispersed manner in the new catalyst. Particles of Pt by itself are no longer detected in the catalyst aged at 980~

816

Table 2 Number, size and composition of the panicles observed using STEM in the wash-coat of new catalyst and of catalysts aged at 900~ or at 980~ Nature of particles State

Characteristics

Pt

Rh

Pt+Rh

CeO2 + Fe203

New

number/30 size (nm) Pt/Rh (1)

8 6-13 -

0 HD (2) -

16 6.5-11 3.6-33.3

6 3-20 -

Aged 16 h at 900~

number 32 size (nm) Pt/Rh (1)

5 2-20

0 -

19 2-40

8 3-50

-

-

number/38 size (nm) Pt/Rh (1)

0

0 -

Aged 16 h at 980~

-

-

1 . 4 - 1 0

24 14-80 1.45-15.

-

14 10-40 -

(1) Atomic ratio (2) HD = hyperdispersed Three CTEM photographs illustrating the particles present in the wash-coat of new catalyst and of catalysts aged at 900~ or at 980~ are shown in Figure 1. The shape of the particles (dark spots) has been taken to be sphere-like and, from the measurement of their diameters, histograms have been plotted representing the percentage of particles of a given size relative to the total number of particles. Figure 1 shows that the particle diameter varies between 0.7 and 16 nm in new catalyst. In catalysts aged at 900 or 980~ the distribution is more heterogeneous, with the sizes varying between 1 and 65 nm or between 1 and 81 nm respectively. It can be seen that in the new catalyst 70% of the particles observed are smaller than 3 nm in size, whereas in catalysts aged at 900~ or at 980~ particles less than 3 nm in size now represent only 30 and 10% of the total, respectively. It is found, furthermore, that the longer the catalyst is aged at high temperature the larger the particle size, but that small-sized particles whose diameter is between 1 and 5 nm still exist in these aged catalysts. This finding is in good agreement with the sintering mechanism known as the "Ostwald ripening

817 as

.= I I 10

0

6

10

1s

20

u

so

88

40

48

Diameter

go

58

oo

M

eo

88

70

715

8o

(nm)

(a)

m

(d) Z

0

6

10

16

20

m

m

u

4o

48

Diameter

60

m

7o

7s

eo

(nm)

(c)

(f)

B-

E16Z lO-

o

6

1o

16

zo

m

11o

M

4o

Diameter

a

m

!

eo

M

7o

~

eo

(nm)

(e)

Figure 1. CTEM photography and diameter histograms for particles present in washcoat a,b: fresh catalyst;c,d: catalyse aged at 900~ catalyst aged at 980~

818 mechanism", which involves the transfer of atoms from the small particles towards the larger ones. Taking into account the size of all the particles observed by CTEM, a calculation was made to estimate the arithmetic mean diameter of these particles, the equivalent diameter deq ' comparable to the mean diameter obtained by chemisorption methods and calculated by comparing surface and volume of the particles, the specific surface area, and the dispersion, which represents the number of accessible metal atoms [14-16]. The results of these various calculations are given in Table 3. Table 3 Number and characteristics of the particles observed by CTEM in the wash-coat of new catalysts and of catalysts aged at 900~ or at 980~ catalyst

ni

d (nm)

deq (nm)

D (%)

new aged 900~ aged 980~

768 513 306

2.9 7.5 12.5

6.2 20.6 42.1

18 6 3

Saged/Snew

0.301 0.147

The equivalent diameter of 6.2 nm observed in the new catalyst is probably an overestimate, due to the existence of particles that are hyperdispersed on the support and that have not been taken into account in these calculations. Furthermore, all these values constitute only an approximation, beating in mind the fact that it has not been possible to distinguish between precious metal particles and particles of Ce and Fe oxides. Nevertheless, these oxide particles were a minority in number, although not insignificant (20 to 37% of the total of the particles analyzed by STEM), and their sizes were comparable to those of the metal particles. 4. OXIDATION OF HYDROCARBONS AT STOICHIOMTRY The degrees of conversion of various C2, C3 and C 6 hydrocarbons are given simultaneously for saturated hydrocarbon and for unsaturated hydrocarbon, in Figures 2a, b and c, as a function of temperature. These determinations were carried out with gaseous mixtures of stoichiometric redox composition and with new catalysts and catalysts aged at 900~ or at 980~

819 These light-off temperatures (T 50 = temperature at which 50% of the hydrocarbon is oxidized) and the mean conversions CM in the 100-600~ range, calculated using the equation below, are given in Table 4. o

I1 C. =

6~176 c zc

Mean conversion:

-

00

C nC dT

CHC

i~

oo d T

O0

When the light-off temperatures of these hydrocarbons are considered, the following ranking is obtained with new catalyst: C3H6>C6 H14>C2H4 ~ C6H6>>>C3H8>>>>C2H6 With catalyst aged at 900~

this ranking becomes:

C6H6 ~ C6H14>C3H6>C2H4>>>>C3H8>>C2H6 and with catalyst aged at 980~ C2H 4 ~ C6H6>C3H6>>>>>C3H8>>C2H6 It can be observed that the difference in reactivity for easy to oxidize compounds decreases when the catalyst ages (the mean activities are of the order of 74% for the catalyst aged at 900~ and of the order of 68% for the catalyst aged at 980~ It is found that the differences in conversion between the easy to oxidize compounds are smaller with aged catalyst than with new catalyst; on the other hand, the difference between the conversions with easy to oxidize compotmds and those that are difficult to oxidize increases appreciably. The drop observed in overall activity can be attributed to a decrease in the number of active sites or may result from a decrease in the individual activity of each site. In the former case the reaction is not "structure-sensitive"; in the latter case, on the other hand, it is. The specific rate (mol.g.m-2.h-1), which varies like the Turn Over Number (TON), can be calculated from the following equation: R = F/S.X, F being the initial molar flow rate of hydrocarbon (mol.h-1), S the specific surface area (m2.g-1) and X the conversion. By arbitrarily choosing the specific surface area of new catalyst as being equal to 1, it is possible to evaluate a relative specific rate for aged catalysts (Figure 3). It is found that, for propane and ethane, R increases with catalyst aging, whereas R decreases for the other hydrocarbons

820

,,

/

#:

I', . . . . ~ ' ~ 1 / , -

I

'*

-"-

Tempe~nare( ' C ' )

lOO ~o 8o

-

Temperluare ('C)

eA

,00'

~l :

c.o

,oj :o,,t 30

fl ~'""*."

I-- "~ I_.... ~.l ~ , ~

j ~ ~;

Figure 2. Aging effect on conversion a. ethane and ethylene oxidation b. propane and propylene oxidation c. hexane and benzene oxidation

Temperature ( ' t ' )

Table 4 Light-off temperatures (T 50) and mean activities CM observed with various hydrocarbons for new and aged catalysts HC

ethane propane hexane ethylene propylen benzene

T50 (~ new

aged at 900~

437 292 197 207 187 207

467 392 222 237 232 219

,,

Mean activity (%) aged at 980~

new

aged at 900~

aged at 980~

547 471

35 62 81 79 83 79

25 45 74 74 74 76

18 29

257 262 257

69 67 68

From this it is consequently deduced that the specific rate increases with the particle size for C3H 8 and C2H6 whereas it decreases for the other hydrocarbons (hexane, ethylene, propylene, benzene). In contrast to CO, for which the specific

821 rate is independent of the particle size [17], the hydrocarbon oxidation reaction is therefore structure-sensitive.

.t

910 ~ 9 A

~ 10

Irnmlj ,~o'c

8

---*--

7

.......... --

7~6 ....

J {

6

,{

cJ

i

Fnnal

o

A~,wC

I "

E t h a n e, , " " *

_~

" .

6A

,..,-'"

"~.m

_

~=/:

__..,.~,..,~r_._-~ ~

200

300

3S0

Temper'amre

4,50

o

,.,,.c

I :

"-''--

AttV~e'C [

....

~,-~l!

~

Propane ,," , -''r'r

.....:;:

:

Propvleoe~

;

..jr* a *"

,.., p" r

'r

o

.

400

' ~'

~-.

I

0 . . . . . .

3

.....,.-_.,,-

I

---o=- Agt.dg0e'C ]

.....

9 '~

-*f ,'

~3

~rm,h

-"5

550

~

600

(oiL')

100

150

20e

~

.300

350

Temperature

400

,150

500

550

(~

9tO ~

-. - ' 2 . 5 "~

"~ ~"

9

Aled 90rC

" "~" " Agtd~10"C

2

Beu.zeue.~ Hexane

e'

$u t.s

-_

Irn~e

""

Alrt'r 90rC

Figure 3. Aging effect on specific rates a. ethane and ethylene b. propane and propylene c. hexane and benzene

~. 0.5 0

-1~

. I$0

200

1.~0

. . 304

.

. 350

Temperature

,SO0

45O

.r

55O

6OO

(*C)

It is known that the oxidation of short-chain alkanes on Pt/ml203 and on Pd/A120 3 is structure-sensitive [18-20]: the Turn Over Number is higher for large particles than for smaller ones. For light alkanes, the increase in the specific rate with particle size which has been observed can be explained by considering the reactivity of the oxygen adsorbed on Pt. The interaction of oxygen with Pt-based supported catalysts has been studied in various laboratories [21-25]. When the Pt is completely dispersed, it is already oxidized to PtO2 at 300~ [21,22]. On the other hand, when it is in the form of larger crystallites, only the surface of these crystallites is oxidized, and this takes place at a higher temperature (500~ [21 ]. Dispersed PtO2 is less active in the hydrocarbon oxidation reaction than Pt covered with oxygen at the surface [21,26]. It is fotmd that, at an identical temperature, oxygen coveting large crystallites is more reactive than oxygen botmd on hyperdispersed Pt. This result leads to believe that the surface of hyperdispersed Pt is then in the form of PtO2, on the other hand, for the large

600

822 particles the oxygen is merely chemisorbed onto the catalyst. This conclusion is similar to that of R.F. Hicks [18]. In the temperature range in which the oxidation of propane and of ethane is initiated on new catalyst (170-377~ and 287-527~ respectively), it may be thought that Pt is oxidized before the hydrocarbons. On the other hand, with aged catalysts, the oxidation of the Pt particles will be progressively less easy (particles of larger size) and consequently proportionally more metallic Pt will remain to activate the oxidation reaction of these hydrocarbons. In contrast to short-chain alkanes, the specific rate for the other hydrocarbons (hexane, ethylene, propylene and benzene) decreases when the particle size increases. It may be concluded that these hydrocarbons react with oxygen before the latter has been able to oxidize the Pt (oxidation temperature of Pt to PtO2 of the order of 300~ for a hyperdispersed catalyst [21,22] and a temperature range where the oxidation is initiated with new catalyst for these compounds are between 157 and 227~ These results disagree with those obtained by L.M. Carballo (propylene oxidation) [27] and with those obtained by A.B. Kooh (heptane oxidation) [28]. In fact, in these two investigations the TONs or the specific rates increase with the particle size. This increase is attributed to a decrease in the fraction of Pt atoms on the ridges and to an increase in these atoms on the terraces [27]. It should be noted, however, that these two investigations, though carried out with catalysts based on Pt or Pd supported on A120 3 or ZrO2, were conducted in the presence of an excess of oxygen and with simple gas mixtures (helium, oxygen and propylene or heptane).

5. INHIBITION EFFECTS

Figure 4a shows the variation in the conversion of propane on new catalyst and on catalyst aged at 900~ as a function of the 02 concentration. It is found that inhibition by 02 in an overall oxidizing gas mixture exists both for new catalyst and for aged catalyst. The conversion maximum is situated in a slightly reducing gas mixture. For hexane and benzene, no inhibition appeared in an oxidizing gas mixture for new catalyst [9,10]. Their removal was already complete at stoichiometry. For aged catalyst, on the other hand, a small decrease in conversion is observed, this is of the order of 5% for hexane and 15% for benzene (Figure 4b).

823 Since inhibition due to oxygen is observed only with the compounds that are difficult to oxidize, it may be attributed to a competition between the chemisorptions of the different compounds. 02 would appear to be adsorbed more rapidly than light alkanes and, as it then covers the whole surface, no more active sites permitting hydrocarbon chemisorption would appear to be let~. In other words, this is equivalent to stating that since the precious metal crystallites are oxidized by 02, propane and ethane would appear to be no longer sufficiently reactive to reduce the crystallites, while the other hydrocarbons are. It may therefore be concluded that short-chain alkanes are oxidized by a mechanism of the Langmuir-Hinshelwood type (the hydrocarbon and oxygen react once they are adsorbed) and that the other compounds can react by a mechanism of the EleyRideal type (unadsorbed hydrocarbon reacts with adsorbed oxygen). iomo-'~w-

I

Propane

>~.

g

0o-

,1,o

e0

np

n,i

e4

As

o~

et

O, Concentration

e,

,9

0o

Io

I:,

oo

oo

ep

(Vol.%)

o.5

oJ

o$

oe

ot

O, Concenlralion

ee

oo

on

! I

t~

13

(Vol.%)

Figure 4. Conversion at 260~ o f propane, hexane and benzene as a funct/on o f O 2 concentration on new catalyst or on catalyst aged at 900~

It has also been observed that the inhibiting effect of oxygen in an oxidizing gas mixture is slightly increased by the addition of 1000 ppm of NO. To verify whether these inhibitions by O2 and NO are rapidly reversible, the following test was performed. The catalyst was first of all placed in contact with a gas mixture with the following composition: 02

NO

CO

H2

C3H8

CO 2

H20

N2

0.77%

480 ppm

0.6%

0.2%

1500 ppmC

10%

10%

78.3%

After this mixture had been passed over the catalyst for 5 minutes, the NO feed was cut off and the conversion of propane was allowed to stabilize for 10 minutes. When it was judged to be stable, the 02 concentration was lowered from

824

0.77% to 0.45% to change over to reducing conditions. Figure 5 shows the result obtained. Qualitatively the same effect is observed for a catalyst aged at 900~ and for the new catalyst. However, the removal of NO increases the propane conversion by only 7%, whereas it increased by approximately 20% with new catalyst. The NO desorption time itself is also shorter (3 minutes instead of 5). From these two points it can be assumed that there is less NO adsorbed on the surface and that consequently the inhibition by NO is less marked than for new catalyst. When the 02 concentration decreases, propane conversion increases by 50% and then drops instantaneously for new catalyst. The same phenomenon is encountered with aged catalyst, except that the increase in conversion is only 30%. As in the case of NO, it may be concluded from this that the inhibition by 02 is less marked for new catalyst than for aged catalyst. The drop in activity of the aged catalyst in oxidizing conditions would not therefore appear to be due to a stronger inhibition by NO and by O2, but indeed to be the consequence of sintering. Likewise, the inhibiting effect of SO2 on the oxidation of hydrocarbons of different types (propane, propene and benzene) was investigated for new catalyst and for catalysts aged at 900~ or 980~ The activities in the presence and absence of SO2 of fresh and aged catalysts are compared in Table 5. 1oo

i

8o ?o

Figure 5. Transient conversion o f propane, as a function o f time, on a catalyst aged at 900~

e9

5._5_.

o

le e

.

0

.

3

.

.

4

.

.

6

.

8

10 Time

12

14

16

18

2O

(rain)

The differences in the light-off temperatures with and without SO 2 are of the order of 10 to 20~ For propylene and benzene, the inhibiting effect observed for tlfis aged catalyst is less marked than for new catalyst [9,10]. The inhibiting effect of SO 2 on alkenes has also been observed [29-31]. The inhibiting effect of SO2 on the oxidation of propylene and benzene can be explained by the competition between these compounds for access to the active sites. In fact, SO2 can already be adsorbed on precious metals at room temperature, (SO2 or SO32-) [32], like hydrocarbons (alkenes and aromatics).

825

Table 5 : Inhibiting effect of $02 on the oxidation of C3Hs, C3H6 and C6H 6 for new Pt+Rh catalyst or catalyst aged for 16 h at 900~ HC

SO2 ppm

T50 (~ new

aged

Mean activity from 1O0 ~. 600~ (%) new aged

C3H8

0 20

292 267

299 309

62 67

53 53

C3H6

0 20

188 224

222 237

83 75

76 73

C6H6

0 20

196 209

219 237

81 78

76 72

On the other hand, the accelerating effect of SO2, seen during the oxidation of propane on new catalyst [9,10], disappears for aged catalyst. A very slight inhibition is found at low conversion and, at high temperature, a slight acceleration of the oxidation of propane by SO2. Overall, it can be said that there is no inhibition or acceleration of the reaction for aged catalyst. For new catalyst the acceleration of the oxidation reaction of short-chain alkanes is due to the formation of new adsorption sites that did not exist in the absence of SO2 [29]. Studies using infrared [30] have shown the presence of sulphates on the alumina support, which are formed by adsorption of SO2 that is already oxidized at 200~ These sulphates could be responsible for the formation of these new sites promoting the dissociative adsorption of short-chain alkanes, resulting in a higher rate of oxidation. These new adsorption sites would appear to be located at the junction between the particles of precious metals and the sulphated support [29]. With aged catalyst these junctions are rarer because of the sintering of the particles. Fewer new sites are therefore formed and thus the acceleration effect is less marked. It can also be assumed that for aged catalyst the oxidation rate of SO2 to SO3 is decreased. Less sulphate would therefore appear to be fonned and consequently the adsorption of alkanes would be less easy. This second hypothesis also makes it possible to explain why the inhibition of propylene and benzene is lower with aged catalyst. Since SO2 is adsorbed less rapidly on aged catalyst, the competition between this compound and the hydrocarbons is consequently reduced and thus the inhibition is less marked.

826 6. CONCLUSION Thermal aging of 3-way catalysts based on Pt+Rh on alumina promoted by Ce and Fe oxides has been followed by examinations using electron microscopy (CTEM and STEM). Three particle populations exist in the wash-coat of catalysts of this type: Pt, Pt/Rh and Ce/Fe. The rhodium that is not associated with the Pt is also detected for new catalyst, but in a form that is hyperdispersed in the atomic state or in the forln of very small particles that are not visible by the CTEM technique. The heat treatments performed (16 h in wet nitrogen at 900 or 980~ result in an increase in the size of the particles, whose mean diameter changes from 3 to 7.5 and then to 12.5 ran. The mixed P t ~ l particles are also enriched in Rh at the expense of the very small Rh particles, which eventually disappear. The activity of this type of catalyst in the oxidation of different hydrocarbons in gas mixtures at stoichiometry was next determined in the new or aged state. Irrespective of the nature of the hydrocarbons, their conversion gradually decreases in keeping with the decrease in metal dispersion. This decrease in conversion can be explained by the loss of active sites when sintering takes place. It has been shown, however, that the oxidation of hydrocarbons is structuresensitive, i.e. that the specific rate relative to the area of the particles is dependent on the size of the latter. These observations are explained by considering the reactivity of oxygen towards Pt crystallites. The larger the particles, the more difficult they are to oxidize. Since metallic Pt is more active than its oxide in catalyzing hydrocarbon oxidation, it is consequently easier to understand that the specific rate increases with particle size. For aged catalyst the inhibition of propane oxidation by nitrogen monoxide and by oxygen is, fiLrthennore, less pronounced in oxidizing conditions. This can be explained by the decrease in the stability of adsorbed oxygen (or of Pt oxide) as a fimction of the increase in the size of the metal particles./xal inhibiting effect of oxygen on the conversion of benzene and hexane in oxidizing conditions was also noted, whereas no such effect existed for new catalyst. Lastly, the effect of SO2 is less marked with catalyst aged at 900~ than with new catalyst. The promoting effect of SO2 on the oxidation of propane no longer exists and the inhibiting effect on the oxidation of propylene and of benzene is less marked. ACKNOWLEDGMENTS The financial support of this research by Octel SA, PSA Peugeot-Citroen, and Renault is gratefidly aknowledged.

827 REFERENCES

1 P. Degobert: "Automobile et Pollution", Ed. Technip, Paris 1992. 2 J.K. Walker, C.L. O'Hara: "Analysis of Automobile Exhaust Gases by Mass Spectrometry", Anal. Chem. 27 (5), 825-828, 1955. 3 E.S. Jacobs: "Rapid Gas Chromatographic Determination of C1 to C10 Hydrocarbons in Automotive Exhaust Gas", Anal. Chem. 38 (1), 43-47, 1966. 4 M.W. Jackson: "Effect of Catalytic Emission Control on Exhaust Hydrocarbon Composition and Reactivity", SAE Teclmical Paper 780624, 1978. 5 D.E. Seizinger, W.F. Marshall, F.W. Cox, M.W. Boyd: "Vehicle Evaporative and Exhaust Emission as Influenced by Benzene Content of Gasoline", SAE Technical Paper 860531, 1986. 6 W.F. Marshall, M.D. Gumey: "Effect of Gasoline Composition on Emission of Aromatic Hydrocarbons", SAE Teclmical Paper 892076. 7 A. Gorse, J.D. Benson, L.J. Painter, V.R. Bums, R.M. Reuter, A.M. Hochlauser, B.H. Ripon: "Toxic Air Pollutant Vehicle Exhaust Emissions with Reformulated Gasolines", SAE Teclmical Paper 912324. 8 B.R. Powell: "/XaaalyticalElectron Microscopy of a Vehicle Aged Automotive Catalyst", Applied Catal., 53,233-250, 1989. 9 J.M. Bart: "Oxydation sur catalyseur trois-voies des diff6rents hydrocarbures et d6riv6s oxyg6n6s pr6sents dans un gaz d'6chappement issu d'un moteur ~i allumage co~mnand6", th6se Nancy, 1992. 10 J.M. Bart, A. Pentenero, M.F. Prigent: "Experimental Comparison Among Hydrocarbons and oxygenated Compounds for their Elimination by ThreeWay Automotive Catalysts", Catalytic Control of Air Pollution-Mobile and Stationary Sources, ACS Symposium Series 495, pp. 42-60, Washington, 1992. 11 R.J. Matyi, H. Schwartz, J.B. Butt: "Particle Size, Particle Size Distribution and Related Measurements of Supported Metal Catalyst". Catal. Rev. - Sci. Eng., 1987, 29 (1), 44-91. 12 H. Dexpert, P. Gallezot, C. Leclercq: "Caract6risation des Catalyseurs par Microscopie Electronique Conventio~melle et Analytique ~ Haute R6solution", les Techniques Physiques d'Etudes des Catalyseurs, Ed. Technip, Paris, 1988, 655-721. 13 A. Rochefort, F. le Peltier: "Les particules M6talliques Support6es", Revue IFP, 46 (2) 1991. 14 P. Duneau : "Effet de support sur la stabilisation du platine en conditions oxydantes", th6se Paris, 1989. 15 G.R. Anderson: "Structure of Metallic Catalyst", Academic Press 1975.

828 16 P. Stonehart: "Electrocatalyst Advances for Hydrocarbon Oxidation in Phosphoric Acid Fuel Cells", J. Hydrogen Energy, 9 (11), 921-928, 1984. 17 J.T. Kurmner: "Use of Noble Metals in Automobile Exhaust Catalysts", J. Plays. Chem. 90 (20), 1986. 18 R.F. Hicks, H. Qi, M.L. Young, R.G. Lee" "Structure Sensivity of Methane Oxidation over Platinum and Palladium", J. Catal. 122, 280-294, 1990. 19 R.F. Hicks, H. Qi, M.L. Young, R.G. Lee: "Effect of Catalyst Structure on Methane Oxidation over Platinum and Palladium", J. Catal. 122, 295-306, 1990. 20 K. Otto, J.M. Andino, C.L. Parks: "The Influence of Platinum Concentration and Particle Size on the Kinetics of Propane Oxidation over Pt/ot Alumina", J. Catal. 131,243-251, 1991. 21 R.W. Mc Cabe, C. Wong, H.S. Woo: "The passivating Oxidation of Platinum", J. Catal. 114, 354-367, 1988. 22 H. Lieske, G. Lietz, H. Spindler, J. Volter: "Reactions of Platinum in Oxygen and Hydrogen Treated Pt/A120 3 Catalysts", J. Catal. 81, 8-16, 1983. 23 C.F. Cullis, B.M. Willat: "Oxidation of Methane over Supported Precious Catalysts", J. Catal. 83,267, 1983. 24 N. Niwa, K. Awano, Y. Murakami: "Activity of supported Catalysts for Methane Oxidation", J. Catal. 7, 317, 1983. 25 R.K. Nandi, F. Molinaro, C. Tang, J.B. Cohen, J.B. Butt, RL.L. Burwell: "The effects of Pretreatment on Structures", J. Catal. 78, 289, 1982. 26 H.C. Yao, M. Sieg, H.K. Plulmner: "Surface Interactions in the Pt/ot A120 3'', J. Catal. 59, 365, 1979. 27 L.M. Carballo, E.E. Wolf: "Crystallite Size Effect during the Catalytic Oxidation of Propylene on Pt/ot A1203", J. Catal., 53,366-373, 1978. 28 A.B. Kooh, W.J. Han, R.G. Lee, R.F. Hicks: "Effect of Catalyst Structure and Carbon Deposition on Heptane Oxidation over Supported Platinum and Palladium", J. Catal. 130, 374-391, 1991. 29 H.S. Gandhi, M. Shelef: "Effect of Sulphur on Noble Metal Automotive Catalyst", Appl. Catal., 77, 175-186, 1991. 30 H.C. Yao, H.K. Stepien, H.S. Gandhi: "The Effects of SO2 on the Oxidation of Hydrocarbons and Carbon Monoxide over Pt/A120 3 Catalyst", J. Catal. 67, 231-236, 1981. 31 V.I. Panchislmyi, N.K. Bondareva, A.V. Sklyarov, V.V. Rozmaov and G.P. Ghadina: "Oxidation of Carbon Monoxide and Hydrocarbons on Platinum and Palladium Catalyst in the Presence of Sulfur Dioxide", Zhumal Prikladdnoi Khilnii, 61 (5), 1093-1098, 1988. 32 C.C. Chang: "Infrared Studies on 3' Alumina", J. Catal. 53,374-385, 1978.


829

SIMULTANEOUS ATMOSPHERE AND TEMPERATURE CYCLING OF THREE-WAY AUTOMOTIVE EXHAUST CATALYSTS

S. Humberta, A. Colina, L. Monceauxa, F. Oudetb and E Courtinea aDdpartement de Gdnie Chimique bService d'Analyse Physico-Chimique, Universitd de Technologie de Compikgne, BP 649, 60206 Compikgne cedex, France

ABSTRACT As an attempt to simulate real operating conditions of automotive converters, a laboratory bench has been designed and ageing procedures determined to reproduce simultaneous chemical and thermal modifications encountered by catalysts in the exhaust line. Characterization of commercial samples after ageing according to different temperature cycles evidences formation of both platinum/rhodium alloys and cubic perovskite-type compound, CeA103. Simultaneously with the formation of cerium aluminate, a thermal stabilization of catalysts is observed, in terms of mean noble metal particles size and concentration of rhodium in alloyed phases. An interpretation based on the crystallographic adaptation of alumina, cerium aluminate and ceria is proposed.

1.1NTRODUCTION

From the automotive industry point of view, study of exhaust catalysts and more particularly their behaviour in varying envirolunents are of primary importance [1]. In this field, laboratory procedures able to simulate operating conditions

830 constitute a practical and economical alternative to motor benches and real driving testing [2-4]. To keep close to realistic condition, i.e., simultaneous thermal and chemical cyclings submitted to converters in the exhaust line, an automated laboratory bench has been specifically designed which can simulate repeated fuel cut-off cycles. In the following are reported characterization results of commercial three-way catalysts after different treatments in this apparatus by means of X-ray diffraction and transmission electron microscopy.

2.EXPERIMENTS

2.1.Samples Samples under study are commercial cordierite honeycomb catalysts. The catalytic washcoat is conventionally composed of ceria-promoted transition alumina-supported 5Pt/1Rh (weight %). Samples are cut from original converters in the form of cylinders of 1 inch (diameter) X 3 inches (length) to meet the geometrical requirements of the experimental set-up (see below). 2.2.Procedures and apparatus Catalysts are systematically treated for four hours under the fifty times repeated identical following cycle: step 1: wanning between low and high temperatures of the cycle under reducing atmosphere step 2: steady state at high temperature; atm.: N2, 10% H20 step 3" cooling to low temperature under oxidizing atmosphere step 4: steady state at low temperature; atm.: N2, 10% H20. To realize temperature variations, samples are placed in a quartz tube (3 inches internal diameter) surrotmded by two adjacent tubular fimaaces. One ftmaace is maintained at the low telnperature of the cycle and contains the catalyst under study. A second one is held at 1200~ and can be rapidly moved in contact with the first one by a pneumatic jack.

831

gases

solenoids valves

quartz tube ~ 1" outlet

~

J 850"C I / fixed oven I

!

i.~

~

jack

flow ratemeter

w~'

Imovmgoven

!

l

oven regulations

1

Figure 1. Schematic representation of the laboratory bench. Samples are placed in a quartz tube in a fixed oven. Moving a second oven determines temperature modification. Simultaneous temperature and atmosphere cycles are automated.

The position of this second oven relatively to the first one determines the high temperature of the cycle. Motion of the second fitrnace and simultaneous atmosphere cyclings are completely automated (TSX-T407 TELEMECANIQUE, GRAFCET progralmning). The space velocity of gases is 20,000h -1. Figure 1 shows a schematic representation of this apparatus. In the present experiments, the low temperature of the cycle is maintained at 850~ and three high temperature differing cycles were tested: 850~ (no , cycle 1), 950~ (cycle 2) and 1050~ (cycle 3). These reference temperatures are measured at the immediate inlet of samples. 2.3.Characterization

X-ray diffraction experiments (XRD) are perfonned on a curve position sensitive detector INEL CPS 120 which allows a simultaneous collection of diffracted beams in the range 5 ~ < 20 < 125 ~ withthe monochrolnatized CuKotl radiation (L=l,5406A, CGR focusing quartz single crystal).

832 Diffractograms are obtained from pure catalytic washcoat (flee of cordierite) after immersion of monoliths in an ultrasonic bath in distilled water and subsequent drying of the resulting suspension. For precise measurements of Xray line positions, ceria (from the catalysts itself) is used as internal standard. Calibration of the detector is perforlned by means of a spline function (DIFFRAC-AT3, SIEMENS/SOCABIM software). Average noble metal particles sizes are determined by X-ray line broadening, corrected for diffractometer magular divergence (Warren-corrected Sherrer's formula (5)). Transmission Electron Microscopy (TEM) is performed on a JEOL JEM 1200EX operated at 120 kV.

3.RESULTS Figure 2 presents a part of typical X-ray diffraction spectra around the (111) reflexion of noble metals for catalysts aged according to cycles 1-3 procedures. Together with these lines are indicated the theoretical positions of the (111) reflexion of pure platinum and rhodium (both fee structures, aPt = 3.924 A and aRh = 3.804 A). Measurement of this line position for treated catalysts, averaged on five samples for each treatment leads to lattice parameters of 3.914 A (cycle 1, Tmax = 850~

3.903 A (cycle 2, Tmax = 950~

and 3.901 N (cycle 3,

Tmax = 1050~ These line shifts suggest the presence of P ~ I alloyed particles in the samples. According to Darling [6], application of Vegard's law [7] allows to evaluate the atomic rhodiuln concentration in alloyed phases. For cycle 1, cycle 2 and cycle 3based procedures, these concentrations are 8%, 17% and 19% respectively. Since the nominal Rh/Pt+Rh atomic ratio of samples is 27%, these results indicate that whereas these two noble metals are completely miscible [6], some rhodium remains unalloyed in catalysts after ageing in the present experimental conditions. Moreover, no significant modification of the rhodiuln concentration in alloyed phases is detected after ageing under cycle 2 and cycle 3 conditions (17% and 19% respectively).

833

!

pt

i 38 ~

i

I

I

39 ~

I

40 ~

i

I

i

i

I

I

41 o

42 ~

Figure 2. X-ray diffraction spectra around the (111) reflexion of noble metals for catalysts aged according to cycles 1 (a), 2 (b) and 3(c) procedures. Lines shifts suggest Pt/Rh alloying. tN

-

0

,

As determined by TEM (figure 3), flesh catalysts present very small noble metals particles size, and an important X-ray line broadening which precludes precise measurement of line positions. It thus appears delicate to determine whether alloying pre-exists or is directly related to the present treatments.

To examinate more precisely the conditions of formation of P t ~ l alloys, the atmosphere cycle was modified, while temperature profile remained unchanged. These experiments reveal Figure 3. ~micrograph offresh catalyst, that in the absence of a reducing atmosphere step (step 1) in the cycle, no X-ray line shift of the Pt (111) reflection can be detected, neither in the case of cycle 1 nor cycle 2 or cycle 3 high temperatures conditions. Formation of Pt/Rh alloys is thus most probably due to the present experimental conditions.

834 Consequently it can be assumed that platinum and rhodium appears mainly as separate dispersed phases in fresh catalysts. X-ray line broadening measurement is a convenient way to derive average noble metal particles size in specific (hkl) crystallographic directions. Because of the very low concentration of noble metals in samples, only the most intense (111) reflexion is detected in diffractograms and can be analyzed in the present work. Table 1 presents these determinations, t111 expressed in nanometers, averaged on five samples, for catalysts tested according to the three different procedures. Together with these data are given the corresponding rhodium atomic concentration in alloyed phases. Table 1 confirms thermal sintering of supported noble metals after exposure to high temperatures. From 5 mn before ageing, catalysts present average particles sizes of 28 nm after treatment according to cycle 3 conditions (Tmax = 1050~ This thermal evolution of supported metal catalysts has been largely reported and analyzed (4, 8-11). However, it should be noted that in the present case, whereas differing by 100~ in their high temperature, cycle 2 (Tmax = 950~ and cycle 3 (Tmax = 1050~ ageing procedures lead to identical mean noble metal particles size (28 nm).

Table 1 Average noble metal particles size (nm) and corresponding rhodium atomic concentration m alloys for fresh and aged catalysts as determmed by XRD. Treatment

Fresh

Cycle 1

Cycle 2

Cycle 3

t111 %Rh

=-750 ~ 25 can fi'om the ~t_~lyst s t ~ e face),

842 the combustion process continues as the exhaust gases travel between the exhaust valve and the catalyst substrate face. This results in a change in the feedgas composition. There should be a conceivable feedgas difference between closecoupled and underfloor applications. In the close coupled application being discussed below, the concentrations of Oxygen and the legislated emission gases 9 Hydrocarbons(HC), carbon monoxide(CO), and oxides of nitrogen(NOx), are all reduced. The resulting proportions may give greater catalyst deactivation than would be expected if the higher exhaust gas temperatures had been achieved by better management of Speed, Load and Spark advance. If the exhaust gas temperatures are relatively low, (

N 2 + O*

+

.

k,,.,

"* N 2 + 2 *

2C0

+ 0 2 --, 2 C 0 2

N2, N 3 : 2 C 0

+ 2NO-)

CO 2 + N 2

where * stands for a catalytic site. Following Oh [13], the 02 adsorption rate is taken proportional to the fraction of vacant sites 8,, rather then the expected 8. 2 dependence. Contrary to Oh the activation energy for the CO desorption and the recombination of two adsorbed N atoms are taken coverage-independent. Two different pathways lead to N2 formation (N2, N3): the recombination of two adsorbed N atoms and the reaction of adsorbed N with adsorbed NO. At low temperatures (< 550 K) the CO-NO reaction kinetics is dominated by the dissociation of NO, while at higher temperatures the recombination of two adsorbed N atoms becomes the dominant path. In this model, the surface of the catalyst can become completely covered with oxygen, in contrast to, e.g. the model of Herz and Marin for the CO oxidation over Pt/AI203 catalyst in which the oxygen surface coverage is limited to 0.5 [14]. Table 2 lists the kinetic parameter values used in this study. Except for the activation energy for CO desorption and the reaction between two adsorbed N atoms, they are identical to those reported by Oh et al. [13].

911

Table 2 Kinetic parameters values used in this study parameter

value

parameter

value

Sco ~

0.5

Edis,

79.4

Ad. 1

1.6"10 TM

Ar.co,

1 "1012

Ea.1

112.0

Eco'

60.0

S o

0.01

AN,.1

2" 109

SNO~

0.5

EN,. 1

87.8

Ad,3

5" 1013

EN,,2

120.0

Ed.3

108.7

AN,.2

3"101~

Aai..

3"101~

Lt

2.7"10 .5

02

Table 3 shows the characteristic times of the elementary reactions in table 1 which indicate at which time scale a reaction proceeds. The calculation of the characteristic times was performed at 505 K and at concentrations corresponding to a stoichiometric inlet composition (table 5). Surface reactions are relatively slow processes when compared to ad- and desorption. Table 3 Definitions and values of the characteristic times of the elementary reactions" characteristic definition time

in )-1

value [s]

characteristic definition time

10

value [s]

..co

(k.coCco

'

Td,co

ka,co1

2.4"10 .3

Tco'

(kco 8o) -1

0.15

Ta,o,

in -1 (2k,.o ~o,)

1.6.10.4

TN,.1

(kN,.18N) -1

7.6

Ta.NO

(k"o.NO"NO/ 9 p.in /-1

1.5"1 0 -5

TN,,2

(2kN, 2) -1

43

Td.NO

ka.NO1

3.5" 10 .3

" 505 K, 8. = 7.6" 10 .4, 8o = 10 .5, 8N = 0.08 3. REACTOR MODEL A one-dimensional model [12] for the isothermal monolith is used which consists of a set of continuity equations for the reactants in the three phases considered: the gas

912

phase, the pores of the washcoat and the catalyst surface. The dependent variables are expressed as C/pf. The continuity equation for reactant i (i = CO, 02 or NO) in the bulk gas phase is given by:

0[c, ! ~ 0 ic, ]

8P,~

~

--m ~-~ ~

- k,.,av(C,.,- C,.,)

(1)

The continuity equation for reactant i in the pores of the washcoat is given by: 4~dw 0 SwP, d~- at

C,.~ I ~ = kf'iav(Cf'i)

C''i)

-

a~"tr~

+ acatrd'i

(2)

The continuity equations for the species CO*, O*, NO*, and N* on the surface are given by: i_t a at 8co = r~176- rd'c~ - rc~

I.t

OSo

at

= 2r~

q aeNO _-

at

r

+ rai,, + rN,.1 - rco'

a, NO

Lt~a-ON = rai,,

(3)

-

-

rd.NO

rN,.1

--

--

rd~,,

-

rN,,

2 rN,.2

(4)

(5)

(6)

The reactor is assumed to operate under steady state conditions before starting any oscillation of the feed. Hence, the initial conditions for the concentration of reactant i in the gas phase and in the pores of the washcoat are: C,.,(x,0) = C,.~"(x) ,

0 _< x _ L

(7)

C,.,(x,0) = C,';'(x) ,

0 _< x _< L

(8)

and for the degree of coverage of the species (j = CO*, O*, NO*, or N*): 8j(x,0) = 8j"(x) ,

0 _< x _< L

(9)

The boundary conditions at x=0 result from the oscillating feed at the inlet of the reactor, for CO given by:

913

C,.co(0,t) : ~f.co[1 + Bsin(2nft)]

(10)

CO is oscillating in counter phase with 02 and NO, so the time dependent feed concentration of 02 and NO is given by: C,.,(0,t) : ~.f., 1 + Bsin(2nft + Values for the parameters of the reactor model are shown in table 4. Table 4. Parameters of the reactor model used in this study (T = 505 K). parameter

value

parameter

value

pf

0.673

av

2.4"103

Cm"up

5.833

dw

2.5" 10-5

kf.co, kf.o,

0.186

L

0.15

kf.NO

0.216

~

0.6

rf.co",rf,o*

1-3"10-4

~w

0.4

1.2" 10.4

ac=

1.25.104

Tf.NO*

' the characteristic time for mass transfer Tf.~ is defined as c/(kf.~av). The model is solved using the same mathematical methods as Lie et al. [12] except for the integration in the x direction, in which collocation with bicubic splines was applied. 4. RESULTS

AND

DISCUSSION

Simulations have been performed with time-invariant and cyclic feeding at typical exhaust gas conditions. The simulations with oscillatory feeding allow a comparison of the time average conversions with the conversions during time-invariant feeding as a function of temperature, frequency, and amplitude. The stoichiometric equivalence ratio of the reactants is defined relative to the stoichiometry of the global reaction: r

:

2Cf o, + t3f NO '

'

(12)

~f, CO

Time-average inlet concentrations and corresponding values of r are given in table 5. Figure 1 shows the steady state gas phase concentrations of the reactants versus the axial reactor coordinate with CO as limiting reactant. Mass transfer limitation is negligible at this temperature, because the production rate of CO2 and the production

914

rate of N2 are low. The concentrations of the reactants in the pores of the washcoat 'follow' the gas phase concentrations at around 95% of their value, and are therefore not shown. The CO conversion near the (~ Of, c0 Of.02 Of, N0 outlet of the reactor is 100%, while the (vol%) (vol%) (vol%) conversion of NO is only 9%. The surface coverages as a function of the axial reactor 0.5 0.6 0.1 0.1 coordinate are shown in figure 2. The 1.0 0.6 0.25 0.1 oxygen coverage does not exceed 10.5 as long as the CO conversion is not complete. 1.5 0.6 0.4 0.1 As shown in figure 3, both the production rates of CO2 and N2 increase towards the outlet of the reactor until the surface 0.80 concentration of CO* becomes zero. The o> o.0o "'~,CO relatively high surface coverage of CO at the t,0 inlet of the reactor is inhibiting the adsorption "~ o.40 of the other reactants and the dissociation of c 0 NO, resulting in low production rates for CO2 C 0.000"20 Cf,N O , .... ~ ..... 0 and N2. Towards the outlet, the adsorption 0.00 0.03 0.06 0.09 0.12 0.15 rate of CO decreases due to the decrease of the gas phase concentration, and as a result axial coordinate [m] more free sites become available for the Figure 1. Gas phase concentrations adsorption of 02 and adsorption and vs. axial coordinate. T = 490 K, dissociation of NO. The resulting higher G = 5.10 .3 kg/s, ~) = 1.5. oxygen coverage, causes the production rate of CO2 to increase, while the increasing ,0o coverage of NO and N leads to a higher 9 o.8o o /I production rate of N2. ~ o.eo Simulation results with cyclic feeding at a 0 /'" i t.,) 0.40 frequency of 0.1 Hz are shown in figures 4-9. 0 J "" " ==~ e . o ........ ~"--"" . , I\ Figure 4 shows the gas phase concentrations at the outlet of the reactor as o.oo 0.00 0.03 0.08 0.09 0.12 0.15 a function of time. The amplitude of the CO oscillation relative to the time average value axial coordinate [ m ] increases from 15% to 76% towards the Figure 2. Surface coverages vs. axial outlet of the reactor, while the amplitude of coordinate. T = 490 K, G = 5.10 .3 NO and 02 decrease from 15% to 10%. The kg/s, ~) = 1.5. maxima in the oxygen oscillation at the reactor inlet turn into minima at the outlet as discussed for CO oxidation over Pt/AI203 by Lie [12]. The surface coverages of CO, O, and NO at the inlet are not shown, but they oscillate in phase with the corresponding gas phase concentrations with amplitudes relative to their time-average values of 7%, 30% and 24%. The surface coverage of N at the inlet oscillates in phase with NO with an amplitude of only 4%. Figure 5 shows the surface coverages at the outlet. The oxygen coverage, which is not shown, oscillates in phase with NO* around a time average value of 1.6.10 -5 and an Table 5 Inlet concentrations and corresponding values of ~).

"

L

/,/

915

amplitude of 151%. The amplitudes of all coverages increase towards the outlet, and Boo, the minima of CO* and the maxima of the ~;~ 1.0e-04 E other species become sharper, leading to relaxation type of oscillations [15]. Figure 6 '~ 5.0e-05 shows the production rate of both CO2 and IO*R. .-N2 at the outlet of the reactor. The steady O.Oe+O0 ' --~ ' ~ 0.00 0.03 0.06 0.09 0.12 0.15 state conversions of CO and NO, are 56% and 7.4% respectively, while the timeaxlal coordinate [ m ] average conversions during cycling of the Figure 3. Production rates of CO2 and feed are 57.5% and 8.9%. N2 vs. axial coordinate. T = 490 K, These differences are explained as follows. G = 5.10 .3 kg/s, r = 1.5. At steady state the high surface coverage of CO causes a relatively low production rate of 0.50 ,..., CO2 and N2. When the gas phase CI,CO "~ 0.40 > concentration of CO increases owing to the 0.30 o"" oscillation, the surface becomes even more II '0.20 occupied with CO*, while the corresponding eCf NO @ (.I decrease of the concentrations of O2 and NO c 0.10 0 0 results in a decrease of the other surface 0.00 0 5 10 15 20 25 30 species. The result is a further decrease of the production rates of CO2 and N2. In time [ s ] contrast, when the CO gas phase Figure 4. Outlet gas phase concentraconcentration is decreased, free sites tions vs. time. T = 505 K, G = 10.2 become available for 02 and NO adsorption kg/s, f = 0.1 Hz, B = 15%, r = 1.0. and for dissociation of NO, with higher production rates as a result. The fact that the 1.00 .-;., CO decrease in the bulk gas is accompanied a) 0.80 eco by an increase of 02 and NO gives an extra a) 0.60 > enhancement of the production rates of CO2 ~ ~\\ ~ ,////~ I ~\ ///~ ii \ o o 0.40 and N2 and hence of the conversions of CO o o m and NO. The positive feedback from the CO 31:: 0.20 -i coverage to the CO gas phase concentration 0.00 0 8 10 15 20 25 30 results in a reinforcement of the CO oscillation whereas the negative feedback time [ s ] from the O and NO coverages to the Figure 5. Outlet surface coverages vs. corresponding gas phase concentrations time. T = 505 K, G = 10.2 kg/s, causes attenuation of the corresponding f = 0.1 Hz, B = 15%, r = 1.0. oscillations. The periodic enhancement of the reaction rates overcompensates the periodic decrease, leading to a positive effect on the time average conversions of both CO and NO when compared with the steady state conversions. This phenomenon is attributed to the non-linear character of the kinetics [16]. The influence of the modulation frequency is discussed in terms of the regimes of operation [16]. According to the characteristic times, the dissociation of NO and the formation of N2 are the first reactions to enter the sliding regime. Simulations showed 1.5o-04

916

that the amplitude of the surface coverage of nitrogen atoms decreased at frequencies 1.ee-04 above 0.1 Hz, meaning that the time-average E 1.2e-04 9 values approach the lower steady state n 0 8.00-06 coverage. Therefore the periodic Q 4.0e-05 enhancement of the production rate of N2 cO L shown in figure 6 disappears, which explains O.Oe+O0 0 5 10 15 20 25 30 the decreasing beneficial effect of oscillating the feed in the frequency range 0.1 - 1 Hz for time [sl NO (figure 7) when comparing the increase Figure 6. Outlet production rates vs. of the time average conversion relative to the time. T = 505 K, G = 10 .2 k g / s , steady state value. The beneficial effect of f = 0.1 Hz, B = 15%, ~) = 1.0. oscillating for CO remains constant, because the coverages of CO and oxygen are still in 0.20 the dynamic regime. The calculated rise NO . o.15 between 1 and 4 Hz is not yet fully X f ~ ~-. understood. Above 1 Hz all surface reactions 0 . 1 0 "~\ / approach operation in the sliding regime, but \\\ / / / \ \ x 0.05 CO \ adsorption/desorption probably is still in the dynamic range causing on-going oscillations o.oo Ii , , of the surface coverage of CO and NO. It 0 2 4 6 8 was noticed, that during the periodically low frequency [ H z ] NO gas phase concentrations NO desorbs Figure 7. T i m e a v e r a g e c o n v e r s i o n s from the surface, especially in the first part of relative to steady state conversions the reactor, which leads to a gradual phase vs. f r e q u e n c y . T = 500 K, G = 10 .2 shift in the NO gas phase oscillation. Above kg/s, B = 15%, r = 1.0. 4 Hz all reactions enter the sliding regime, ultimately resulting in steady state conversions. Larger amplitudes enhance the I advantage of the cyclic feeding at 0.1 Hz 0.30 "/ (figure 8) up to 30% for NO and 8% for CO. o,o Higher amplitudes cause periodic 0.10 ~" - x z f/ _ t . - ~CO stoichiometric limitations by CO resulting in 0.00 ~ decreasing time average conversions. Higher -0.10 0.10 0.20 0.30 0.40 0.s0 temperatures are beneficial when oscillating amplitude [-] the feed (figure 9) as long as the local CO conversion is incomplete during a cycle. This Figure 8. Time average conversions is in contrast to CO oxidation in the absence relative to s t e a d y s t a t e c o n v e r s i o n s of NO [12], where beneficial effects were vs. amplitude. T = 500 K, G = 10.2 only observed at temperatures below the k g / s , f = 0.1 Hz, ~ = 1.0. light-off. This was attributed to the comparable steady state degrees of coverage by CO and oxygen at high temperatures. The presence of NO causes much lower degree of coverage by oxygen over the complete temperature range of interest. Further increase of temperature again leads to stoichiometric limitation by CO during a larger fraction of the cycle time, ultimately leading to time-average conversions below the steady state conversions. 2.0e-04

i,-,, ~)

~176 jjlj j/

I

917

CONCLUSIONS

0.30 | X

0.20

/. / /

\\NO \

Oscillatory feeding increases the timeaverage conversions of both CO and NO relative to the steady state values until -0.10 \ CO periodic complete conversion of CO occurs. \ -0.20 \ \ The enhancement can be explained by -0.30 soo slo s20 sao s40 sso 490 strongly changed surface coverages during cyclic feeding compared to steady state temperature [K] values. A maximum enhancement of the NO Figure 9. Time average conversions conversion is obtained at a modulation relative to steady state conversions frequency of 0.1 and 4 Hz. The CO vs. the temperature. G = 10.2 kg/s, conversion is rather frequency independent. f = 0.1 Hz, B = 15%, ~) = 1.0. Larger amplitudes and higher temperatures enhance the positive effects of cyclic feeding, as long as no stoichiometric limitations X

0.10

jJ

0.00

occur.

SYMBOLS Roman letters ac= av A B C db dw EA f G k,.~ kd.~ kf.~ k, L r R S~ t T x X

catalytic surface area per unit reactor volume geometric surface area per unit reactor volume pre-exponential factor amplitude in percentage of CQ~" concentration internal diameter of channel thickness of washcoat activation energy frequency mass flow adsorption coefficient for species i desorption coefficient for species i mass transfer coefficient for species i reaction rate coefficient reactor length mole Rh per unit catalytic surface area reaction rate gas constant sticking coefficient for component i time temperature axial coordinate conversion

2

mRh mR-3 m~2 mR-3

% mol mf3 mR mR kJ mo1-1 Hz kg s 1 mf 3 mo1-1 s 1 s-1 mf-3 m~2 s ~ s -1 mR mol mRh-2 mol m ' 2 R h s'l kJ moll K s K mR

918

Greek letters E:w

0 Pf

(~msup T

void fraction of monolith washcoat porosity surface coverage gas density stoichiometric equivalence ratio superficial mass flow characteristic time

m f 3 mR 3 m f 3 m w -3

mol mOIRh-1 kg mf3 kg mR2

Subscripts

Superscripts

a cat d f i s w

in ss tavg

adsorption catalytic surface area desorption bulk gas phase referring to reactant i or interface pores in the washcoat washcoat

S "1

inlet steady state time average

REFERENCES o

2. .

4. 5. 6. ~

o

.

10. 11. 12. 13. 14. 15. 16.

M.B. Cutlip, AIChE J., 25(3) (1979) p.502-508 G. Vaporciyan, A. Annapragada, E. Gulari, Chem. Eng. Sci., 43(11) (1988) p. 2957-2966 X. Zhou, E. Gulari, Chem. Eng. Sci., 41(4) (1986) p.883-890 X. Zhou, Y. Barshad, E. Gulari, Chem. Eng. Sci., 41(5) (1986) p. 1277-1284 R.C. Graham, D.T. Lynch, AIChE J., 36(12) (1990) p.1796-1806 J.C. Schlatter, R.M. Sinkevitch, P.J. Mitchell, Ind. Eng. Chem. Prod. Res. Dev., 22 (1983) p. 51-56 R.K. Herz, J.B. Kiela, J.A. Sell, Ind. Eng. Chem. Prod. Res. Dev., 22 (1983) p. 387-396 K.C. Taylor, R.M. Sinkevitch, Ind. Eng. Chem. Prod. Res. Dev., 22 (1983) p.45-51 B.K. Cho, Ind. Eng. Chem. Res., 27 (1988) p. 30-36 B.K. Cho, L.A. West, Ind. Eng. Chem. Fundam., 25 (1986) p. 158-164 J.A. Moulijn, F. Kapteijn, Chemisch Magazine (1989) p. 499-501 A.B.K. Lie, J. Hoebink, G.B. Marin, Chem. Eng. J., 53 (1993) p. 47-54 S.H. Oh, G.B. Fisher, J.E. Carpenter, D.W. Goodman, J. Catal., 100 (1986) p.360-376 R.K. Herz, S.P. Marin, J. Catal., 65 (1980) p. 281-296 P. Gray, S.K. Scott, Chemical Oscillations and Instabilities, Oxford Science Publications, 1990 Yu.Sh. Matros, Catalytic Processes Under Unsteady-state Conditions, Elsevier, Amsterdam, 1989

A. Frennet and J.-M. Bastin (Eds.) Catalysis attd Automotive Pollution Control 111 Studies in Surface Science and Catalysis, Vol. 96 9 1995 Elsevier Science B.V. All rights reserved.

919

COLD START HYDROCARBON EMISSIONS CONTROL VIA ADMIXING THREE WAY CONVERSION CATALYSTS WITH HEAT EXCHANGE AND HYDROCARBON ADSORPTION PHENOMENA

P.L. Burk, a J.K. Hochmuth, a D.R. Anderson, a S. Sung," A. Punke, b U. Dahle, b S.J. Tauster, a C.O.Tolentino," J. Rogalo, a G. Miles, a M. Mignano" and M. Niejako a ~Engelhard Corporation, 101 W o o d Avenue, Iselin, N e w Jersey 08830,U.S.A.

bEngelhard Teclmologies GmbH & Co. OHG, Hamaover, Germany ABSTRACT The revisions in the United States Clean Air Act of 1990 and recent regulatory actions taken by the California Air Resources Board and European Economic Community require the development of automobiles with much lower tail pipe emissions. A significant portion of the total pollutants emitted to the atmosphere by motor vehicles occurs immediately following the startup of the engine when the engine block and exhaust manifold are cold, and the catalytic converter has not yet reached high conversion efficiencies. To meet these stringent, mandated emission levels, new technologies must be created that attack these "cold start" pollutants. One intriguing strategy for handling cold start emissions employs hydrocarbon adsorbers. The sorber scavenges and withholds hydrocarbons from the exhaust gas until the catalyst becomes active, then the hydrocarbons are released and burned on the catalyst. Recent advances in materials technology have uncovered non-carbon-based sorbent alternatives to the classic carbon-based beds. These solids also trap via a physical interaction between the hydrocarbons and the scavenging constituent, but display better thermal stability, especially in the presence of oxygen. To take advantage of these new hydrocarbon scavenging constituents, an auto exhaust system known as the Low Hydrocarbon Emissions System (LHES) composed of a catalyzed heat exchanger and hydrocarbon trap has been designed and tested. The system was custom fitted onto several 1993 vehicles with a variety of engine management strategies. In each case U.S. FTP 75 total hydrocarbon emissions were reduced between 45 - 75% versus the vehicle's stock exhaust system. The LHES system also proved resistant to an accelerated thermal aging that was equivalent to 50,000 miles. A deactivation factor for all pollutants of 1.0 was calculated for the LHES following a 75 hr engine test bed aging with the heat exchanger inlet gas temperature set at 760~

920 1. INTRODUCTION

Over the next decade and in several regions of the world, vehicle emission regulations will become so stringent that Three Way Conversion (TWC) catalystonly exhaust systems will not be sufficient to meet these standards. The reason is simple. During the time it takes for the exhaust gas to bring a TWC catalyst from room temperature to an active state, i.e., somewhere in excess of 300~ pollutants escape to the atmosphere untouched. Such "cold start" emissions found in the U.S. FTP 75 and European tests account for >60% of all the hydrocarbons (HC's) emitted by the vehicle [1], and overwhelm a vehicle's chance for meeting California Air Resources Board's Low Emission Vehicle (LEV) or Ultra Low Emission Vehicle (ULEV) targets (Table 1). Diverse teclmologies for lowering these cold start hydrocarbon emissions can be found in the literature including exhaust gas burners [2 - 4], exhaust gas igniters [5 - 7] , and electrically heated catalysts [8 - 13] These teclmologies reduce the time it takes for a catalyst to reach light-off temperature by the injection of either chemical or electrical energy into the gas flow upstream of the TWC catalyst.

Table 1 California's Low Emission Vehicle Program Certification Standards FTP (grams/mile)" Category ~

NMOG b

CO

NOx

TLEV LEV ULEV ZEV

0.125 0.075 0.040 0.000

3.4 3.4 1.7 0.0

0.4 0.2 0.2 0.0

Emissions after 50,000 miles b NMOG = Nomnethane organic gases including oxygenated species LEV = transition low emission vehicle; LEV = low emission vehicle; ULEV= ultra low emission vehicle; and ZEV = zero emission vehicle

921 An alternate strategy for dealing with cold start HC's makes use of HC traps. A HC trap first scavenges HC's fi'om the cold exhaust via a physical adsorption process until catalyst light-off occurs, then returns the HC's to the activated catalyst wherein they are burned to CO2 and 1-120. Since the HC adsorption and desorption for reliable traps are physical processes [14, 15], the rate of HC release from a trap depends both on inlet gas HC concentration and gas temperature. Several HC trap-based system patents and papers have recently surfaced, and make use of bypass valves for controlling when the exhaust flow is directed through or around the HC trap [16 - 20]. In each case the effectiveness of the design depends on reliably delivering at just the right time the trapped HC's to a hot, active TWC catalyst. Figure 1 shows a typical sequence for a valvebased system. During the cold start period, the exhaust gas flows untouched through the TWC catalyst and into the trap where the HC's are scavenged and held Once the catalyst heats up and begins converting the pollutants, the valves switch and the exhaust bypasses the HC trap. In the next step, the trap is purged so that the HC's reenter the gas stream in front of the TWC catalyst.

(a) |C~176STaRt! .........................................................

..,.."

Engme.=,-]l~ TWC ~

..

Air Valve ~

Tailpipe

Valve .......... Trap ....-~. Valve ~

Taill~Pe

Valve

~ Trap ~

;. ............................................

(b) l w,,.M,o.o, I Engine-,-,.~ TWC ~

I

Figure 1. An exhaust system fitted with valves and a HC adsorber located downstream of the TWC catalyst bed. (a) During coM start operation, the exhaust gas flow passes through the TWC and into the HC trap wherein HC's are removed and held. (b) After TWC light-off the valves switch and the exhaust gas bypasses the HC trap, and the trap is purged mto the TWC bed. In this paper we report on how heat exchange teclmology can be married to HC trap technology to give an auto exhaust system free of valves. Figure 2

922 shows such a system with a heat exchanger composed of two TWC catalyst beds in heat exchange relation and a HC trap. When the exhaust system is cold, the exhaust gas stream passes through the first catalyst bed then into the HC trap. The trap scavenges the HC's as in a valved system. The scrubbed gas returns to the heat exchanger, passes through the cold second catalyst bed and then out the tail pipe As the exhaust system heats up, the first TWC catalyst bed undergoes normal light-of. The cleaned gas exits the heat exchanger and then sweeps the HC's out of the HC Trap. At the same time the HC trap releases the HC's, the first pass TWC catalyst bed has been transferring heat via conduction to the second catalyst bed. The HC's purged from the trap reenter the heat exchanger and encounter a hot, activated TWC catalyst bed wherein they are converted to carbon dioxide and water. Our successful merging of hydrocarbon trap and heat exchanger teclmologies has resulted in a simple, passive Low Hydrocarbon Emissions System (LHES) able to transform diverse 1993 vehicles into either Low Emission or Ultra Low Emission Vehicles. Previously, we described a rudimentary heat exchanger prototype/hydrocarbon trap system on an eight year old 1985 2.3 L Volvo 740 GLE that gave an FTP-75 0.065 g/mile NMOG, a fresh LEV performance [21 ]. HEATEXCHANGER TAIL PIPE ,

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